JPH0542763B2 - - Google Patents
Info
- Publication number
- JPH0542763B2 JPH0542763B2 JP60096073A JP9607385A JPH0542763B2 JP H0542763 B2 JPH0542763 B2 JP H0542763B2 JP 60096073 A JP60096073 A JP 60096073A JP 9607385 A JP9607385 A JP 9607385A JP H0542763 B2 JPH0542763 B2 JP H0542763B2
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- film
- conductive film
- tin oxide
- substrate
- 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
Links
Classifications
-
- 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
Landscapes
- Liquid Crystal (AREA)
- Physical Vapour Deposition (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Photovoltaic Devices (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Surface Treatment Of Glass (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は液晶表示板や太陽電池等の透明電極に
好適な低抵抗透明導電膜を生成する方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a low resistance transparent conductive film suitable for transparent electrodes of liquid crystal display panels, solar cells, etc.
［従来の技術］
従来、液晶表示板や、太陽電池等の透明電極に
用いる透明導電膜としては、酸化錫膜（例えばネ
サ膜）または酸化インジウムを主成分としたITO
膜が広く用いられている。[Prior Art] Conventionally, as transparent conductive films used for transparent electrodes of liquid crystal display boards and solar cells, tin oxide films (for example, NESA films) or ITO containing indium oxide as the main component have been used.
Membranes are widely used.
［発明が解決しようとする課題］
酸化錫による透明導電膜は一般に塩化錫にドー
パントとして塩化アンチモンを添加した膜生成組
成物を使用してCVD法により膜生成させるが、
このCVD法では膜厚を均一にすることが困難で
ある上、膜生成過程で塩化水素が発生するため公
害処理設備を必要とする等の問題がある。最近、
提案されている真空蒸着法やスパツタリング法等
の物理的生成方法により生成した酸化錫透明導電
膜はCVD法による欠点をもたないが、導電膜の
比抵抗はITO膜には及ばない。またITO膜は比抵
抗が10-4のオーダーを示し抵抗値が低いという長
所はあるが、特に太陽電池の透明電極として用い
た場合には、ITO膜中のインジウム（In）が太陽
電池の内部に拡散し、光電変換効率を低下させた
り、寿命を短くしたりする等の問題がある。[Problems to be Solved by the Invention] A transparent conductive film using tin oxide is generally formed by a CVD method using a film forming composition in which antimony chloride is added as a dopant to tin chloride.
With this CVD method, it is difficult to make the film thickness uniform, and hydrogen chloride is generated during the film formation process, so there are problems such as the need for pollution treatment equipment. recently,
The tin oxide transparent conductive film produced by the proposed physical production method such as vacuum evaporation method or sputtering method does not have the drawbacks of CVD method, but the specific resistance of the conductive film is not as good as that of ITO film. In addition, although ITO film has the advantage of having a specific resistance of the order of 10 -4 and a low resistance value, especially when used as a transparent electrode in a solar cell, indium (In) in the ITO film is There are problems such as a decrease in photoelectric conversion efficiency and a shortened lifespan.
本発明の目的は均一な膜厚を再現性良く容易に
得ることができて、公害の虞れがない真空蒸着法
やスパツタリング法によつて、ITO膜がもつ問題
点を有しない低抵抗酸化錫透明導電膜を生成する
方法を提案することにある。 The object of the present invention is to produce a low-resistance tin oxide film that does not have the problems of ITO films by using a vacuum evaporation method or sputtering method that can easily obtain a uniform film thickness with good reproducibility and that does not cause any risk of pollution. The purpose of this invention is to propose a method for producing a transparent conductive film.
［課題を解決するための手段］
本発明の低抵抗透明導電膜の生成方法は、活性
化反応真空蒸着法、イオンプレーテイング真空蒸
着法またはマグネトロンスパツタリング法により
低抵抗透明導電膜を生成する方法である。[Means for Solving the Problems] The method for producing a low resistance transparent conductive film of the present invention includes producing a low resistance transparent conductive film by an activation reaction vacuum deposition method, an ion plating vacuum deposition method, or a magnetron sputtering method. It's a method.
活性化反応真空蒸着法により低抵抗透明導電膜
を生成する本発明の方法においては、酸化錫に
0.5〜10重量％（全量に対する重量％）の酸化タ
ンタルを添加してなる膜生成用組成物を蒸発材料
として用い、基板温度を100〜400℃、酸素分圧を
１×10-4〜５×10-4Torr、高周波電力を10〜
200wとして前記膜生成用組成物を蒸発させ、蒸
着速度を0.05〜10Å／秒として前記基板上に膜生
成させる。 In the method of the present invention for producing a low-resistance transparent conductive film by activation reaction vacuum evaporation method, tin oxide is
A film forming composition containing 0.5 to 10% by weight (based on the total amount) of tantalum oxide was used as the evaporation material, the substrate temperature was 100 to 400°C, and the oxygen partial pressure was 1×10 -4 to 5×. 10 -4 Torr, high frequency power 10~
The film forming composition is evaporated at 200 W, and a film is formed on the substrate at a deposition rate of 0.05 to 10 Å/sec.
イオンプレーテイング真空蒸着法により低抵抗
透明導電膜を生成する本発明の方法においては、
酸化錫に0.5〜10重量％の酸化タンタルを添加し
てなる膜生成用組成物を蒸発材料として用い、基
板温度を80〜400℃、酸素分圧を１×10-4〜５×
10-4Torr、高周波電力を10〜200wとして前記酸
化錫及び酸化タンタルを蒸発させ、直流バイアス
電圧を−100〜−1000V、蒸着速度を0.05〜10
Å／秒として前記基板上に膜生成させる。 In the method of the present invention for producing a low resistance transparent conductive film by ion plating vacuum evaporation method,
A film forming composition prepared by adding 0.5 to 10% by weight of tantalum oxide to tin oxide was used as the evaporation material, the substrate temperature was 80 to 400°C, and the oxygen partial pressure was 1 x 10 -4 to 5 x.
The tin oxide and tantalum oxide were evaporated at 10 -4 Torr and high frequency power of 10 to 200 W, with a DC bias voltage of -100 to -1000 V and a deposition rate of 0.05 to 10.
A film is formed on the substrate at a rate of Å/sec.
またマグネトロンスパツタリング法により低抵
抗透明導電膜を生成させる本発明の方法において
は、酸化錫に５〜18重量％の酸化タンタルを添加
した膜生成用組成物を陰極物質として用い、基板
温度を100〜400℃、酸素分圧を１×10-4〜７×
10-4Torrとして陰極物質をスパツタさせ、膜生
成速度を10〜30Å／秒として前記基板上に膜生成
させる。 In addition, in the method of the present invention in which a low-resistance transparent conductive film is produced by magnetron sputtering, a film-forming composition in which 5 to 18% by weight of tantalum oxide is added to tin oxide is used as a cathode material, and the substrate temperature is 100 to 400℃, oxygen partial pressure 1×10 -4 to 7×
The cathode material is sputtered at 10 -4 Torr to form a film on the substrate at a film formation rate of 10 to 30 Å/sec.
［作用］
酸化錫に酸化タンタルを添加しない膜生成用組
成物を用いて生成した透明導電膜の比抵抗値は、
10-2Ωcmのオーダーであるが、上記のように酸化
錫に酸化タンタルを添加した膜生成用組成物を用
いると、透明導電膜の比抵抗値を10-3〜10-4Ωcm
のオーダー低い値にすることができた。[Function] The specific resistance value of a transparent conductive film produced using a film-forming composition in which tantalum oxide is not added to tin oxide is:
The specific resistance value of the transparent conductive film is on the order of 10 -2 Ωcm, but when using a film forming composition in which tantalum oxide is added to tin oxide as described above, the specific resistance value of the transparent conductive film can be reduced to 10 -3 to 10 -4 Ωcm.
could be made to an order of magnitude lower.
また本発明の方法では、CVD法によらずに、
物理的生成法（真空蒸着法またはスパツタリング
法）により膜を生成できるため、塩化水素が発生
することがなく、公害問題を生じない。更に物理
的生成法により膜を生成するため、膜厚を均一に
することができる。 In addition, in the method of the present invention, without using the CVD method,
Since the film can be produced by a physical production method (vacuum evaporation method or sputtering method), no hydrogen chloride is generated and no pollution problem occurs. Furthermore, since the film is produced using a physical production method, the film thickness can be made uniform.
更にまた、本発明の方法によると、インジウム
を含まない低抵抗透明導電膜を得ることができる
ため、従来の透明導電膜（ITO膜）を太陽電池に
適用した場合に生じていた問題点（光電変換効率
の低下及び寿命の短縮）を解決することができ
る。 Furthermore, according to the method of the present invention, it is possible to obtain a low-resistance transparent conductive film that does not contain indium. (decreased conversion efficiency and shortened lifespan) can be solved.
［実施例］
以下図面を参照して本発明の実施例を説明す
る。[Examples] Examples of the present invention will be described below with reference to the drawings.
実施例 １
透明導電膜を生成するための膜生成用組成物と
して、酸化錫に酸化タンタルをドーパントとして
添加したものを用い、活性化反応真空蒸着法によ
り、ガラス基板上に酸化錫透明導電膜を生成させ
た。Example 1 A tin oxide transparent conductive film was formed on a glass substrate by an activation reaction vacuum deposition method using tin oxide with tantalum oxide added as a dopant as a film forming composition for producing a transparent conductive film. generated.
第１図は本実施例で用いた真空蒸着装置の構成
の概略を示したもので、同図において１は接地さ
れているベース、２はベース１の上に伏せた状態
で着脱可能に配置されてフランジ部２ａにより気
密保持が図られた釣鐘状のチヤンバであり、ベー
ス１及びチヤンバ２は接地されている。ベース１
にはバルブ３及び４を介してガス導入管５及び排
気管６が接続され、これらガス導入管５及び排気
管６の一端はチヤンバ２内に開口している。ガス
導入管５の他端には図示しない流量制御部を介し
て酸素ガスボンベ及びアルゴンガスボンベのガス
供給源が接続されている。排気管６の他端には図
示しない真空ポンプ等の排気装置が接続され、こ
の排気装置を駆動することによりチヤンバ２内を
真空状態にすることができるようになつている。
またチヤンバ２内は図示しないリークバルブによ
り外気と連通させ得るようになつている。 Figure 1 schematically shows the configuration of the vacuum evaporation apparatus used in this example. In the figure, 1 is a grounded base, and 2 is a base 1 that is removably placed face down on the base 1. It is a bell-shaped chamber that is kept airtight by a flange portion 2a, and the base 1 and chamber 2 are grounded. base 1
A gas introduction pipe 5 and an exhaust pipe 6 are connected to the chamber 2 through valves 3 and 4, and one ends of these gas introduction pipe 5 and exhaust pipe 6 are opened into the chamber 2. Gas supply sources such as an oxygen gas cylinder and an argon gas cylinder are connected to the other end of the gas introduction pipe 5 via a flow rate control section (not shown). An evacuation device such as a vacuum pump (not shown) is connected to the other end of the exhaust pipe 6, and by driving this evacuation device, the inside of the chamber 2 can be brought into a vacuum state.
Further, the inside of the chamber 2 can be communicated with outside air through a leak valve (not shown).
チヤンバ２内のベース１上には、電子ビーム発
生器７が設置されている。この電子ビーム発生器
７は、その上部にペレツト装填用凹部７ａを備
え、該凹部内には、酸化錫（SnO2）酸化タンタ
ル（Ta2O5）を0.5〜10重量％添加した膜生成用
組成物（蒸発材料）８のペレツトが装填されてい
る。 An electron beam generator 7 is installed on the base 1 within the chamber 2 . This electron beam generator 7 has a recess 7a for loading pellets in its upper part, and in the recess is a film-forming material containing 0.5 to 10% by weight of tin oxide (SnO 2 ) and tantalum oxide (Ta 2 O 5 ). Pellets of composition (evaporation material) 8 are loaded.
チヤンバ２内の上部には、相対向させて配置さ
れた平行平板からなる高周波放電電極９，９が取
付けられている。高周波放電電極９，９の一方
は、ベース１を気密に貫通させて取付けられたブ
ツシングＢを通して高周波の高電圧を出力する高
周波電源１０に接続され、他方は接地されてい
る。チヤンバ２内の高周波電極９，９の上方のペ
レツト装填用凹部７ａに対向する位置に大径の貫
通孔（図示せず）を有する基板ホルダ１１が設け
られている。この基板ホルダ１１はブツシングＢ
及びスイツチS2を介して直流のバイアス電源１４
の負電極に接続され、バイアス電源１４の正電極
は接地されている。また、基板ホルダ１１はスイ
ツチS1を介して接地できるようになつている。基
板ホルダ１１の上にはガラス等の基板１２が載置
される。 At the upper part of the chamber 2, high-frequency discharge electrodes 9, 9 made of parallel flat plates arranged to face each other are attached. One of the high-frequency discharge electrodes 9, 9 is connected to a high-frequency power source 10 that outputs a high-frequency high voltage through a bushing B that is attached to the base 1 in an airtight manner, and the other is grounded. A substrate holder 11 having a large diameter through hole (not shown) is provided in the chamber 2 at a position above the high frequency electrodes 9, 9 and facing the pellet loading recess 7a. This board holder 11 is a bushing B.
and a DC bias power supply 14 via switch S 2
The positive electrode of the bias power supply 14 is grounded. Further, the substrate holder 11 can be grounded via a switch S1 . A substrate 12 made of glass or the like is placed on the substrate holder 11 .
基板ホルダ１１の上方には基板１２を加熱する
ためのヒータ１３が設けられ、このヒータは図示
しない電源に接続されている。 A heater 13 for heating the substrate 12 is provided above the substrate holder 11, and this heater is connected to a power source (not shown).
電子ビーム発生器７はその側面から電子ビーム
EBを発射するように構成され、発射された電子
ビームEBは電子ビーム発生器７に内蔵された図
示しない偏向コイルにより偏向されてペレツト装
填用凹部７ａ内に装填された膜生成用組成物８に
入射するようになつている。 The electron beam generator 7 emits an electron beam from its side.
The emitted electron beam EB is deflected by a deflection coil (not shown) built in the electron beam generator 7, and is applied to the film forming composition 8 loaded into the pellet loading recess 7a. It is becoming incident.
本実施例では、上記の真空蒸着装置を用いて、
先ず電子ビーム発生器７のペレツト装填用凹部７
ａ内に膜生成用組成物（蒸発材料）を填装し、ガ
ラス基板１２を基板ホルダ１１の上に載置した。
次いでチヤンバ２をベース１の上に載置してバル
ブ３を閉じ、排気管６に接続した図示しない排気
装置によりチヤンバ２内を真空状態にした。チヤ
ンバ２内が所定の真空状態になつた時にヒータ１
３に通電して基板１２を昇温させ、基板１２の温
度が100〜400℃となり、チヤンバ２内の真空度が
４×10-6Torr以下になつた時にガス導入管のバ
ルブ３を開いてチヤンバ２内に酸素ガスとアルゴ
ンガスとの混合ガスを導入した。この場合、チヤ
ンバ２内の酸素ガスの分圧を１×10-4〜５×
10-4Torr、アルゴンガスの分圧を３×10-4〜１
×10-3Torrとし、高周波放電電極９，９間に10
〜200Wの高周波電力を供給すると共に、スイツ
チS2を開き、スイツチS1を閉じて基板ホルダ１１
を接地した。そして電子ビーム発生器７を作動さ
せて電子ビームEBを発生させ、該電子ビームに
より膜生成用組成物８を加熱蒸発させて基板１２
の下面に酸化錫の透明導電膜を生成させた。この
場合、基板１２に透明導電膜が、0.05〜10Å／秒
の蒸着速度で生成されるように膜生成用組成物８
を蒸発させた。 In this example, using the above vacuum evaporation apparatus,
First, the pellet loading recess 7 of the electron beam generator 7
A film-forming composition (evaporation material) was loaded into the chamber a, and the glass substrate 12 was placed on the substrate holder 11.
Next, the chamber 2 was placed on the base 1, the valve 3 was closed, and the inside of the chamber 2 was brought into a vacuum state by an exhaust device (not shown) connected to the exhaust pipe 6. When the chamber 2 reaches a predetermined vacuum state, the heater 1
3 to raise the temperature of the substrate 12, and when the temperature of the substrate 12 reaches 100 to 400℃ and the degree of vacuum in the chamber 2 becomes 4×10 -6 Torr or less, open the valve 3 of the gas introduction pipe. A mixed gas of oxygen gas and argon gas was introduced into chamber 2. In this case, the partial pressure of oxygen gas in chamber 2 is set to 1×10 -4 to 5×
10 -4 Torr, partial pressure of argon gas 3×10 -4 ~1
×10 -3 Torr, and 10
While supplying ~200W of high frequency power, open switch S 2 and close switch S 1 to connect substrate holder 11.
was grounded. Then, the electron beam generator 7 is operated to generate an electron beam EB, and the film forming composition 8 is heated and evaporated by the electron beam, so that the substrate 12 is heated and evaporated.
A transparent conductive film of tin oxide was formed on the bottom surface of the . In this case, the film forming composition 8 is applied so that a transparent conductive film is formed on the substrate 12 at a deposition rate of 0.05 to 10 Å/sec.
was evaporated.
所定の膜厚の透明導電膜が生成された後、ヒー
タ１３への通電を停止させて基板１２の温度を下
げ、図示しないリークバルブから外気を流入させ
てチヤンバ２内を大気圧に戻し、チヤンバ２をベ
ース１から外して基板１２を取出した。 After a transparent conductive film with a predetermined thickness is formed, the power supply to the heater 13 is stopped to lower the temperature of the substrate 12, and outside air is introduced from a leak valve (not shown) to return the inside of the chamber 2 to atmospheric pressure, and the chamber 2 is then closed. 2 was removed from the base 1 and the board 12 was taken out.
本実施例では、酸化錫に添加する酸化タンタル
のドーパント量を０〜12重量％の範囲で種々変え
て上記の操作を繰返し行い、膜厚が200Åの透明
導電膜を生成してその比抵抗値を測定した。その
結果ドーパント量（全量に対する重量％）に対す
る比抵抗（Ωcm）の特性は第２図の曲線ａの通り
で、比抵抗の最低値は約８×10-4Ωcmであつた。
なお、この場合の測定値は○印でプロツトしてあ
る。 In this example, the above operation was repeated by varying the amount of tantalum oxide dopant added to tin oxide in the range of 0 to 12% by weight to produce a transparent conductive film with a thickness of 200 Å, and its specific resistance value was measured. As a result, the characteristics of the specific resistance (Ωcm) with respect to the amount of dopant (% by weight relative to the total amount) were as shown in the curve a in FIG. 2, and the lowest value of the specific resistance was about 8×10 -4 Ωcm.
Note that the measured values in this case are plotted with circles.
第２図の曲線ａから明らかなように、酸化タン
タルのドーパントを用いない場合の比抵抗は1.1
×10-2Ωcmであるのに対し、酸化タンタルのドー
パントを用いることにより、比抵抗を10-3〜
10-4Ωcmオーダーに引下げ得ることが明らかにな
つた。また本発明の透明導電膜生成粗生物を用い
て得られた酸化物透明導電膜と、ドーパントを添
加しないで得られた酸化物透明導電膜とについて
透過率を測定した所、両者の間に透過率の差はな
く、酸化タンタルを加えたことによる透過率の低
下は認められなかつた。 As is clear from curve a in Figure 2, the specific resistance when no tantalum oxide dopant is used is 1.1.
×10 -2 Ωcm, but by using tantalum oxide dopant, the resistivity can be reduced to 10 -3 ~
It became clear that it could be lowered to the order of 10 -4 Ωcm. In addition, when the transmittance was measured for the oxide transparent conductive film obtained using the transparent conductive film producing crude product of the present invention and the oxide transparent conductive film obtained without adding a dopant, it was found that the transmittance between the two was There was no difference in transmittance, and no decrease in transmittance was observed due to the addition of tantalum oxide.
第２図から明らかなように、酸化タンタルのド
ーパントを添加して比抵抗値を１桁乃至２桁低下
させる効果を出すためには、酸化タンタルのドー
パント量を0.5〜10重量％の範囲に設定する必要
がある。特に、ドーパント量を４％とした場合に
最も低い比抵抗値（約８×10-4Ωcm）を得ること
ができる。 As is clear from Figure 2, in order to achieve the effect of reducing the resistivity by one to two orders of magnitude by adding a tantalum oxide dopant, the amount of tantalum oxide dopant must be set in the range of 0.5 to 10% by weight. There is a need to. In particular, when the amount of dopant is 4%, the lowest specific resistance value (approximately 8×10 -4 Ωcm) can be obtained.
このように、酸化錫に0.5〜10重量％の酸化タ
ンタルをドーパントとして添加して活性化反応真
空蒸着法により膜生成させると、膜厚が均一でし
かも従来の酸化錫透明導電膜より１桁乃至２桁比
抵抗値が低い低抵抗酸化錫透明導電膜を得ること
ができる。 In this way, when a film is formed by adding 0.5 to 10% by weight of tantalum oxide as a dopant to tin oxide and using the activation reaction vacuum evaporation method, the film thickness is uniform and one order of magnitude thicker than the conventional tin oxide transparent conductive film. A low-resistance tin oxide transparent conductive film with a two-digit low specific resistance value can be obtained.
実施例 ２
本実施例では第１図と同様の装置を用い、実施
例１で用いたものと同一の膜生成用組成物８を用
いて、基板ホルダー１１に負の直流バイアスをか
けるイオンプレーテイング真空蒸着法により透明
導電膜を生成した。Example 2 In this example, an apparatus similar to that shown in FIG. 1 was used, and the same film forming composition 8 as used in Example 1 was used to perform ion plating in which a negative DC bias was applied to the substrate holder 11. A transparent conductive film was produced by vacuum evaporation.
このイオンプレーテイング真空蒸着法により透
明導電膜を生成する場合には基板温度を80〜400
℃の範囲に設定する。酸素ガス分圧、アルゴンガ
ス分圧及び蒸着速度は活性化反応真空蒸着法によ
る場合と同様である。また高周波放電電極９，９
間に供給する高周波電力も10〜200Wと、活性化
反応真空蒸着法による場合と同様であるが、イオ
ンプレーテイング真空蒸着法による場合には、ス
イツチS1を開くとともにスイツチS2を閉じて電極
９，９間に−100〜−1000Vの直流バイアス電圧
を印加する。イオンプレーテイング法により透明
導電膜を生成した場合のドーパント量に対する透
明導電膜の比抵抗値の特性は実施例１と同様に第
２図の曲線ａの通りであり、この場合の測定値は
△印でプロツトしてある。従つて比抵抗値を１桁
乃至２桁低下させる効果を得るために必要なドー
パント量の範囲は実施例１の場合と同様である。
またこの場合も、得られた透明導電膜の透過率は
従来の酸化錫透明導電膜の透過率と同様であり、
酸化タンタルを加えたことによる透過率の低下は
認められなかつた。 When producing a transparent conductive film using this ion plating vacuum evaporation method, the substrate temperature should be set at 80 to 400.
Set to a range of ℃. The oxygen gas partial pressure, argon gas partial pressure, and deposition rate are the same as those in the activation reaction vacuum deposition method. Also, high frequency discharge electrodes 9, 9
The high frequency power supplied between the electrodes is 10 to 200 W, which is the same as when using the activation reaction vacuum evaporation method, but when using the ion plating vacuum evaporation method, switch S 1 is opened and switch S 2 is closed to connect the electrodes. Apply a DC bias voltage of -100 to -1000V between 9 and 9. When a transparent conductive film is produced by the ion plating method, the characteristic of the specific resistance value of the transparent conductive film with respect to the amount of dopant is as shown by the curve a in FIG. 2, as in Example 1, and the measured value in this case is △ It is plotted with a mark. Therefore, the range of the amount of dopant necessary to obtain the effect of reducing the resistivity by one or two orders of magnitude is the same as in Example 1.
Also in this case, the transmittance of the obtained transparent conductive film is similar to that of the conventional tin oxide transparent conductive film,
No decrease in transmittance was observed due to the addition of tantalum oxide.
実施例 ３
本実施例では、真空蒸着法に代えて、マグネト
ロンスパツタリング法により前記と同一の膜生成
組成物を用いて透明導電膜を生成させた。Example 3 In this example, a transparent conductive film was produced using the same film-forming composition as described above by a magnetron sputtering method instead of a vacuum evaporation method.
本実施例では、基板の温度を100〜400℃とし、
酸素ガス分圧を１×10-4〜７×10-4Torr、膜生
成速度を10〜30Å／秒とした。そして酸化錫に酸
化タンタルをドーパントとして添加した膜生成組
成物を陰極として用い、該陰極と陽極との間に電
圧を印加して陰極物質（膜生成組成物）をスパツ
タさせることにより基板上に透明導電膜を生成さ
せた。この場合、酸化錫に添加する酸化タンタル
のトーパント量を種々変えて透明導電膜を生成す
る実験を行つたところ、トーパント量に対する膜
の比抵抗値の特性は第２図の曲線ｂに示す通りで
あつた。同曲線から明らかなように、ドーパント
を添加しない場合の比抵抗は４×10-2Ωcmであつ
たが、酸化タンタルのドーパント量を５〜18重量
％とした場合に１桁乃至２桁低い、10-3〜10-4Ω
cmのオーダーの比抵抗値を有する低抵抗導電膜を
得ることができた。ドーパント量を10重量％とし
た場合に最も低い比抵抗値（約９×10-4Ωcm）を
得ることができた。またこの場合も透過率の低下
は認められなかつた。 In this example, the temperature of the substrate is 100 to 400℃,
The oxygen gas partial pressure was 1×10 −4 to 7×10 −4 Torr, and the film formation rate was 10 to 30 Å/sec. Then, a film-forming composition in which tantalum oxide is added as a dopant to tin oxide is used as a cathode, and a voltage is applied between the cathode and an anode to sputter the cathode material (film-forming composition) onto a transparent substrate. A conductive film was produced. In this case, when we conducted an experiment to produce a transparent conductive film by varying the amount of tantalum oxide dopant added to tin oxide, the characteristics of the specific resistance value of the film with respect to the amount of dopant were as shown in curve b in Figure 2. It was hot. As is clear from the same curve, the specific resistance was 4×10 -2 Ωcm when no dopant was added, but it was one to two orders of magnitude lower when the amount of tantalum oxide dopant was 5 to 18% by weight. 10-3 to 10-4 Ω
We were able to obtain a low-resistance conductive film with a specific resistance value on the order of cm. When the amount of dopant was 10% by weight, the lowest specific resistance value (approximately 9×10 −4 Ωcm) could be obtained. Also in this case, no decrease in transmittance was observed.
以上の実施例１、２、３で明らかなように、酸
化錫に酸化タンタルをトーパントとして添加した
ものを膜生成用組成物として透明導電膜を生成さ
せると、基板温度、酸素ガス分圧、アルゴンガス
分圧及び蒸着速度または膜生成速度の適当な条件
を選ぶことにより、高透光性、低抵抗の酸化錫透
明導電膜が得られる。そしてこの透明導電膜の比
抵抗は10-3乃至10-4のオーダーであり、同じ面積
抵抗の透明導電膜を得るのであれば、比抵抗値が
10-2のオーダーの従来の酸化錫透明導電膜を用い
る場合に比べてその膜厚を１／10と非常に薄くす
ることができる。このことは透過率の向上にもつ
ながり、従来より透過率が高く、しかも生産性の
優れた透明導電膜を供給することが可能となる。 As is clear from Examples 1, 2, and 3 above, when a transparent conductive film is produced using a film-forming composition in which tantalum oxide is added as a dopant to tin oxide, the substrate temperature, oxygen gas partial pressure, argon By selecting appropriate conditions for gas partial pressure and vapor deposition rate or film formation rate, a tin oxide transparent conductive film with high light transmittance and low resistance can be obtained. The specific resistance of this transparent conductive film is on the order of 10 -3 to 10 -4 , and if a transparent conductive film with the same area resistance is obtained, the specific resistance value is
The film thickness can be extremely thinned to 1/10 of that of a conventional tin oxide transparent conductive film of the order of 10 -2 . This also leads to an improvement in transmittance, making it possible to supply a transparent conductive film with higher transmittance than before and with excellent productivity.
また、上記のように酸化錫に所定量の酸化タン
タルを添加した膜生成用組成物を用いて真空蒸着
法またはスパツタリング法により透明導電膜を生
成すれば、酸化錫に対する酸化タンタルの含有比
率を所定の値に設定することにより所定量の酸化
タンタルが添加された透明導電膜を簡単に得るこ
とができる。この場合、有害なガスが発生する等
の公害問題が生じないので、公害防止の為の設備
が不要になり、従来の膜生成用設備をそのまま用
いて従来より優れた特性を有する低抵抗透明導電
膜を得ることができる。 Furthermore, if a transparent conductive film is produced by a vacuum evaporation method or a sputtering method using a film-forming composition in which a predetermined amount of tantalum oxide is added to tin oxide as described above, the content ratio of tantalum oxide to tin oxide can be adjusted to a predetermined value. By setting the value to , it is possible to easily obtain a transparent conductive film to which a predetermined amount of tantalum oxide is added. In this case, pollution problems such as the generation of harmful gases do not occur, so there is no need for equipment for pollution prevention, and conventional film production equipment can be used as is to create a low-resistance transparent conductor with superior properties than before. membrane can be obtained.
［発明の効果］
以上のように、本発明の生成方法によれば、酸
化錫に所定量の酸化タンタルを添加したものを膜
生成用組成物として用いることによつて、膜厚が
均一で比抵抗値が極めて低い酸化錫による低抵抗
透明導電膜を得ることができる。[Effects of the Invention] As described above, according to the production method of the present invention, by using tin oxide with a predetermined amount of tantalum oxide added as a film production composition, a uniform film thickness can be obtained. A low-resistance transparent conductive film made of tin oxide and having an extremely low resistance value can be obtained.
また本発明の低抵抗透明導電膜の生成方法によ
れば、酸化錫に対する酸化タンタルの含有比率を
適当に設定して膜生成用組成物を蒸発またはスパ
ツタさせるだけで容易に低抵抗透明導電膜を得る
ことができる。また、この方法を実施するにあた
つては、有害ガスの発生がなく公害防止のための
設備を必要としないため、従来の膜生成用設備を
そのまま利用して、または従来の膜生成用設備と
同様の設備により、従来より優れた特性を有する
透明導電膜を得ることができるという利点があ
る。 Furthermore, according to the method for producing a low-resistance transparent conductive film of the present invention, a low-resistance transparent conductive film can be easily produced by simply setting the content ratio of tantalum oxide to tin oxide appropriately and evaporating or sputtering the film-forming composition. Obtainable. In addition, when implementing this method, it does not generate harmful gases and does not require equipment for pollution prevention, so it is possible to use conventional film production equipment as is or use conventional film production equipment. There is an advantage that a transparent conductive film having properties superior to those of the conventional method can be obtained using equipment similar to the above.
更に本発明の方法によれば、インジウムを含ま
ない低抵抗透明導電膜を得ることができるため、
従来の透明導電膜（ITO膜）を太陽電池に適用し
た場合に生じていた問題点（光電変換効率の低下
及び寿命の短縮）を解決することができる利点が
ある。 Furthermore, according to the method of the present invention, it is possible to obtain a low resistance transparent conductive film that does not contain indium.
It has the advantage of being able to solve the problems (decreased photoelectric conversion efficiency and shortened lifespan) that occurred when conventional transparent conductive films (ITO films) were applied to solar cells.
第１図は真空蒸着法により本発明の透明導電膜
を生成する場合の蒸着装置の概略構造を示す断面
図、第２図は酸化錫に添加する酸化タンタルのド
ーパント量に対する透明導電膜の比抵抗の特性を
示した線図である。
２……チヤンバ、５……ガス導入管、６……排
気管、７……電子ビーム発生器、９……高周波放
電電極、１２……基板、１３……ヒータ。
Figure 1 is a cross-sectional view showing the schematic structure of a vapor deposition apparatus for producing the transparent conductive film of the present invention by vacuum evaporation, and Figure 2 is the specific resistance of the transparent conductive film with respect to the amount of tantalum oxide dopant added to tin oxide. FIG. 2...Chamber, 5...Gas introduction pipe, 6...Exhaust pipe, 7...Electron beam generator, 9...High frequency discharge electrode, 12...Substrate, 13...Heater.
Claims (1)
活性化反応真空蒸着法により生成させる低抵抗透
明導電膜の生成方法において、酸化錫に0.5〜10
重量％の酸化タンタルを添加してなる膜生成用組
成物を蒸発材料として用い、基板温度を100〜400
℃、酸素分圧を１×10-4〜５×10-4Torr、高周
波電力を10〜200Wとして前記膜生成用組成物を
蒸発させ、蒸着速度を0.05〜10Å／秒として前記
基板上に膜生成させることを特徴とする低抵抗透
明導電膜の生成方法。 ２ 基板上に酸化錫を主成分とする透明導電膜を
イオンプレーテイング真空蒸着法により生成させ
る低抵抗透明導電膜の生成方法において、酸化錫
に0.5〜10重量％の酸化タンタルを添加してなる
膜生成用組成物を蒸発材料として用い、基板温度
を80〜400℃、酸素分圧を１×10-4〜５×
10-4Torr、高周波電力を10〜200Wとして前記酸
化錫及び酸化タンタルを蒸発させ、直流バイアス
電圧を−100〜−1000V、蒸着速度を0.05〜10
Å／秒として前記基板上に膜生成させることを特
徴とする低抵抗透明導電膜の生成方法。 ３ 基板上に酸化錫の透明導電膜をマグネトロン
スパツタリング法により生成させる低抵抗透明導
電膜の生成方法において、酸化錫に５〜18重量％
の酸化タンタルを添加した膜生成用組成物を陰極
物質として用い、基板温度を100〜400℃、酸素分
圧を１×10-4〜７×10-4Torrとして陰極物質を
スパツタさせ、膜生成速度を10〜30Å／秒として
前記基板上に膜生成させることを特徴とする低抵
抗透明導電膜の生成方法。[Scope of Claims] 1. A method for producing a low-resistance transparent conductive film in which a transparent conductive film containing tin oxide as a main component is produced on a substrate by an activation reaction vacuum deposition method, wherein tin oxide contains 0.5 to 10% of tin oxide.
A film forming composition containing % by weight of tantalum oxide was used as the evaporation material, and the substrate temperature was set at 100 to 400.
℃, the oxygen partial pressure was 1×10 -4 to 5×10 -4 Torr, and the high frequency power was 10 to 200 W to evaporate the film forming composition, and the deposition rate was 0.05 to 10 Å/sec to form a film on the substrate. 1. A method for producing a low-resistance transparent conductive film. 2. A method for producing a low-resistance transparent conductive film in which a transparent conductive film containing tin oxide as a main component is produced on a substrate by ion plating vacuum evaporation method, in which 0.5 to 10% by weight of tantalum oxide is added to tin oxide. Using the film-forming composition as an evaporation material, the substrate temperature was 80 to 400°C, and the oxygen partial pressure was 1 x 10 -4 to 5 x.
The tin oxide and tantalum oxide were evaporated at 10 -4 Torr and high frequency power of 10 to 200 W, with a DC bias voltage of -100 to -1000 V and a deposition rate of 0.05 to 10.
A method for producing a low resistance transparent conductive film, characterized in that the film is produced on the substrate at a rate of Å/sec. 3. In a method for producing a low-resistance transparent conductive film in which a transparent conductive film of tin oxide is produced on a substrate by magnetron sputtering, 5 to 18% by weight of tin oxide is added.
A composition for film formation to which tantalum oxide has been added is used as a cathode material, and the cathode material is sputtered at a substrate temperature of 100 to 400°C and an oxygen partial pressure of 1 x 10 -4 to 7 x 10 -4 Torr to form a film. A method for producing a low-resistance transparent conductive film, comprising forming the film on the substrate at a rate of 10 to 30 Å/sec.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60096073A JPS61256506A (en) | 1985-05-08 | 1985-05-08 | Low resistance transparent conductive film and generation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60096073A JPS61256506A (en) | 1985-05-08 | 1985-05-08 | Low resistance transparent conductive film and generation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61256506A JPS61256506A (en) | 1986-11-14 |
| JPH0542763B2 true JPH0542763B2 (en) | 1993-06-29 |
Family
ID=14155227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60096073A Granted JPS61256506A (en) | 1985-05-08 | 1985-05-08 | Low resistance transparent conductive film and generation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61256506A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007055231A1 (en) * | 2005-11-09 | 2007-05-18 | Mitsui Mining & Smelting Co., Ltd. | SnO2 SPUTTERING TARGET AND PROCESS FOR PRODUCING SAME |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009205799A (en) * | 2006-06-06 | 2009-09-10 | Asahi Glass Co Ltd | Transparent conductive film, method of manufacturing the same, and sputtering target used for its manufacture |
| US7452488B2 (en) | 2006-10-31 | 2008-11-18 | H.C. Starck Inc. | Tin oxide-based sputtering target, low resistivity, transparent conductive film, method for producing such film and composition for use therein |
| KR101630118B1 (en) * | 2014-03-07 | 2016-06-13 | 주식회사 엘지화학 | Light modulation device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4065743A (en) * | 1975-03-21 | 1977-12-27 | Trw, Inc. | Resistor material, resistor made therefrom and method of making the same |
| JPS5537804A (en) * | 1978-09-05 | 1980-03-17 | Tokyo Shibaura Electric Co | Door unit for enclosed switchboard |
| NL8303183A (en) * | 1983-09-15 | 1985-04-01 | Philips Nv | METHOD FOR APPLYING A TRANSPARENT COAT ON A SUBSTRATE |
-
1985
- 1985-05-08 JP JP60096073A patent/JPS61256506A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007055231A1 (en) * | 2005-11-09 | 2007-05-18 | Mitsui Mining & Smelting Co., Ltd. | SnO2 SPUTTERING TARGET AND PROCESS FOR PRODUCING SAME |
| JP2007131891A (en) * | 2005-11-09 | 2007-05-31 | Mitsui Mining & Smelting Co Ltd | SnO2-based sputtering target and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61256506A (en) | 1986-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4931158A (en) | Deposition of films onto large area substrates using modified reactive magnetron sputtering | |
| CN1826423B (en) | Transparent conductive oxides | |
| EP0385475A2 (en) | Method of forming a transparent conductive film | |
| CN101294272A (en) | Method for room temperature sputtering deposition of indium tin oxide transparent conductive film on flexible substrate | |
| US4428810A (en) | Method and apparatus for depositing conducting oxide on a substrate | |
| US3991228A (en) | Deposition of tin oxide films on glass | |
| KR100336621B1 (en) | Method of depositing an io or ito thin film on polymer substrate | |
| KR930001782B1 (en) | Manufacturing method of transparent conductive film and apparatus for manufacturing same | |
| JPH0542763B2 (en) | ||
| CN114990476B (en) | Nitrogen-doped tetrahedral amorphous carbon film and preparation method and application thereof | |
| JPH02101160A (en) | Ion plating method | |
| JP2000038654A (en) | Production of substrate with transparent electrically conductive film, substrate with transparent electrically conductive film and liquid crystal displaying element | |
| JPH11335815A (en) | Substrate with transparent conductive film and deposition apparatus | |
| JP4170507B2 (en) | Method for producing transparent conductive film | |
| US4415602A (en) | Reactive plating method and product | |
| JPH058527B2 (en) | ||
| JP3453329B2 (en) | Transparent conductive film and method for manufacturing the same | |
| CN115142033A (en) | Non-stoichiometric alumina material and preparation method thereof | |
| JPH0273963A (en) | Formation of thin film on low-temperature substrate | |
| JPH07107809B2 (en) | Method for producing transparent conductive film | |
| JPH02189816A (en) | Method for forming transparent conductive film | |
| JP3095232B2 (en) | Method for producing transparent conductive film | |
| JPS61292817A (en) | Formation of transparent conducting metal oxide film | |
| JPH0723532B2 (en) | Method for forming transparent conductive film | |
| JPS63121653A (en) | Formation of transparent conductive film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |