JPS59117273A - Manufacture of transparent conductive film - Google Patents
Manufacture of transparent conductive filmInfo
- Publication number
- JPS59117273A JPS59117273A JP57226405A JP22640582A JPS59117273A JP S59117273 A JPS59117273 A JP S59117273A JP 57226405 A JP57226405 A JP 57226405A JP 22640582 A JP22640582 A JP 22640582A JP S59117273 A JPS59117273 A JP S59117273A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- film
- gas
- conductive film
- oxygen gas
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 23
- 238000004544 sputter deposition Methods 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000007769 metal material Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000005546 reactive sputtering Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052786 argon Inorganic materials 0.000 abstract description 6
- 229910052718 tin Inorganic materials 0.000 abstract description 6
- 229910052738 indium Inorganic materials 0.000 abstract description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005361 soda-lime glass Substances 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000005354 aluminosilicate glass Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、反応性スパッタリングによる透明導電膜の製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a transparent conductive film by reactive sputtering.
一般に、可視光領域において透明で、かつＳ電性を有す
る透明導電膜は、液晶ディスプレイ、ＥＬディスプレイ
など新しいディスプレイ方式における透明電極や、アモ
ルファスシリコン太陽電池における透明電極として使用
され、またフォトマスクの帯電防止のための透明ガラス
基板上に成膜して使用されている。In general, transparent conductive films that are transparent in the visible light region and have S conductivity are used as transparent electrodes in new display systems such as liquid crystal displays and EL displays, and as transparent electrodes in amorphous silicon solar cells. It is used by forming a film on a transparent glass substrate for prevention purposes.
これ等の透明導電膜は、インジウム、スズ、アンチモン
又はこれ等の合金、あるいは酸化物などから成る金属材
料をターゲットとして、アルゴンなどの不活性ガスと酸
素ガスなどの活性ガスを含む混合ガス中でスパッタリン
グ法により透明基板上に成膜される。These transparent conductive films target metal materials such as indium, tin, antimony, their alloys, or oxides, in a mixed gas containing an inert gas such as argon and an active gas such as oxygen gas. A film is formed on a transparent substrate by a sputtering method.
この成膜時の透明導電膜は、透明度が高いものについて
は抵抗値が可なり大きいために、大気中に熱処理するこ
とにより、抵抗値を小さくさせている。Since the transparent conductive film at the time of film formation has a considerably high resistance value if it is highly transparent, the resistance value is reduced by heat treatment in the atmosphere.
スパッタリングにおける酸素ガス濃度と成膜速度との関
係は、酸素ガス濃度が小→大になるに従って、成膜速度
が大→小に移行するが、その場合、ターゲット表面は酸
素ガス濃度が小のとき未酸化状態になり、その酸素ガス
濃度がある値を越えるど、酸化が急激に進行して高抵抗
の酸化膜となることから、従来のスパッタリング条件と
しては、ターゲット表面に酸化膜が形成される直前の状
態で行なわれていた。The relationship between oxygen gas concentration and film formation rate in sputtering is that as the oxygen gas concentration increases from small to large, the film formation rate changes from large to small. When the target becomes unoxidized and its oxygen gas concentration exceeds a certain value, oxidation rapidly progresses to form a high-resistance oxide film. Therefore, under conventional sputtering conditions, an oxide film is formed on the target surface. This was done in the previous state.
しかしながら、この状態は、酸素ガス濃度の微減に対し
て成膜速度が急激に増大し、透過率が急激に低くなって
不透明になる欠点があった。また逆に、酸素ガス濃７、
度の微増に対して比抵抗が急激に増大づる欠点があった
。その結果、この状態でのスパッタリング法はその条件
の制御が困難であり、所望な透明導電膜を成膜させる点
で量産性に欠けていた。However, this state has the disadvantage that the film formation rate increases rapidly in response to a slight decrease in the oxygen gas concentration, and the transmittance rapidly decreases, resulting in opacity. Conversely, oxygen gas concentration 7,
The drawback was that the resistivity increased rapidly with a slight increase in temperature. As a result, it is difficult to control the conditions of the sputtering method in this state, and it lacks mass productivity in terms of forming a desired transparent conductive film.
本発明の目的は、以上の欠点を除去した透明導電膜の製
造方法を提供することであり、すなわち、第１の目的は
、スパッタリング条件の制御を容易にして、量産性を向
上させた透明導電膜の製造方法を提供することであり、
第２の目的は、比抵抗の小さい透明導電膜の製造方法を
提供することである。An object of the present invention is to provide a method for manufacturing a transparent conductive film that eliminates the above-mentioned drawbacks. That is, the first object is to provide a transparent conductive film that facilitates control of sputtering conditions and improves mass productivity. To provide a method for manufacturing a membrane,
The second objective is to provide a method for manufacturing a transparent conductive film with low specific resistance.
このような目的を達成させるために、本発明による透明
導電膜の製造方法は、透明導電膜用金属材料をターゲラ
１〜とし、スパッタガスを不活性ガスと酸素ガスを含む
混合ガスにし、前記酸素ガスの濃度によって前記ターゲ
ットの表面を未酸化層状態に設定して反応性スパッタリ
ングにより、前記金属材料を透明基板上に成膜した後、
大気中又は酸化性雰囲気中で３００〜５００℃にて熱処
理し、次に冷却することを特徴としている。ここで、［
透明導電膜用金属材料」としては、インジウム、スズ、
アンチモンなどの金属材料が挙げられる。In order to achieve such an object, the method for producing a transparent conductive film according to the present invention uses Targetera 1 as the metal material for the transparent conductive film, uses a mixed gas containing an inert gas and oxygen gas as the sputtering gas, and uses the oxygen gas as the sputtering gas. After forming the metal material on the transparent substrate by reactive sputtering with the surface of the target set in an unoxidized layer state depending on the concentration of the gas,
It is characterized by heat treatment at 300 to 500°C in air or an oxidizing atmosphere, and then cooling. here,[
Metal materials for transparent conductive films include indium, tin,
Examples include metal materials such as antimony.
「不活性ガス」としては、アルゴン、ネオン、クリプト
ン、キセノンなどのガスが挙げられる。Examples of the "inert gas" include gases such as argon, neon, krypton, and xenon.
「透明基板」としては、ソーダライムガラス、アルミノ
シリケートガラス、ボロンシリケートガラス、石英ガラ
スなどが挙げられる。「酸化性雰囲気」としては、酸素
ガス、二酸化炭素ガス、前記不活性ガス及び／または窒
素に酸素を含む混合ガスなどが挙げられる。Examples of the "transparent substrate" include soda lime glass, aluminosilicate glass, boron silicate glass, and quartz glass. Examples of the "oxidizing atmosphere" include oxygen gas, carbon dioxide gas, the above-mentioned inert gas, and/or a mixed gas containing nitrogen and oxygen.
次に、スパッタリングにおける酸素ガスＩｉ１度と成膜
速度の関係を説明する。第１図は酸素ガス流量と成膜速
度の関係を示す特性図であり、横軸は酸素流＠ （Ｓ
ＣＣＭ ： Ｓ ｔａｎｄａｒｄ ｃｕｂｉｃ ｃ
ｅｎｔｉｍｃｔｅｒ ｐｅｒ ＋ｎ１ｌｌＵｔｅ＝
１気圧、２５℃の状態での１分間当りの流１ｉ （Ｑ
Ｃ） ） 、縦軸は成膜速度である。なお、不活性ガス
として流量７０８０ ＣＭのアルゴンを使用し、同図中
、曲線ａはスパッタリング電流１ｓｐ＝０．’７Ａ、曲
線すはＩ ｓｐ＝ １ 、’５Ａ及び曲線Ｃは１ｓｐ＝
２．５Ａに設定している。Next, the relationship between the oxygen gas Ii 1 degree and the film formation rate in sputtering will be explained. Figure 1 is a characteristic diagram showing the relationship between oxygen gas flow rate and film formation rate, and the horizontal axis is oxygen flow @ (S
CCM: Standard cubic c
entimcter per +n1llUte=
Flow 1i (Q
C) ), the vertical axis is the deposition rate. Incidentally, argon was used as the inert gas at a flow rate of 7080 CM, and in the figure, curve a indicates a sputtering current of 1sp=0. '7A, curve I sp= 1, '5A and curve C 1 sp=
It is set to 2.5A.
従来のスパッタリング条件は、前述したとおりターゲッ
ト表面に酸化膜が形成される直前の状態、すなわち曲線
ａ、ｂ及びＣにおいてそれぞれａｌ、１）＋及びＣ＋の
各点近傍にて成膜していたために、各点より僅かだけ酸
素流量が少なくなった場合、成膜速度が急激に増大し、
透明な膜から茶色ないし脚色を呈した膜になって、透過
率が極端に低下し、一方、各点より僅かだけ酸素流量が
多くなった場合、透過率は変わらないものの、比抵抗が
３桁程度高くなってしまう。As mentioned above, the conventional sputtering conditions were such that the film was formed in the state just before the oxide film was formed on the target surface, that is, in the vicinity of the points al, 1)+, and C+ on curves a, b, and C, respectively. , when the oxygen flow rate is slightly lower than at each point, the deposition rate increases rapidly,
The transparent film changes to a brown or colored film, and the transmittance drops dramatically.On the other hand, when the oxygen flow rate increases slightly from each point, the transmittance remains the same, but the resistivity decreases by three orders of magnitude. The level will be higher.
したがって、従来のスパッタリング条件は、各点におけ
る酸素ガス流量の許容量を極めて少なくしなければなら
ず、点ａ１にて±０．５３ＣＣＭ程度、点ｂ１にて±０
．３ＳＣＣＭ程度、点ｃ１にて±０．３８ＣＣＭ弱にし
なければならない。このように許容量を少なくすること
は、当然にして酸素ガス流量のコントロールを制約させ
ることになってしまう。また、その許容量を比較的多く
した場合、すなわち点ａ１にて±０．５８ＣＣＭの場合
には、スパッタリング電流が比較的小さいことがら、成
膜速度が低くなってしまう。Therefore, in conventional sputtering conditions, the permissible amount of oxygen gas flow rate at each point must be extremely small, approximately ±0.53 CCM at point a1 and ±0 at point b1.
．． It has to be about 3SCCM, a little less than ±0.38CCM at point c1. Reducing the allowable amount in this way naturally limits the control of the oxygen gas flow rate. Furthermore, when the allowable amount is relatively large, that is, ±0.58 CCM at point a1, the sputtering current is relatively small, so the film formation rate becomes low.
一方、本発明では、酸素ガス濃度とターゲラ１−表面に
酸化層が形成されない、すなわち未酸化層状態に酸素ガ
ス濃度を′設定して反応性スパッタリングにより成膜す
ることから、８曲１ｍａ 、 ｂ及びＣにおいて、ａｚ
□ａｂ、ｂｌ〜ｂ）及びｃ２〜ｃ５の間の領域、すなわ
ち〃［容量としてはそれぞれ１〜８８ＣＣＭ、２〜２０
３ ＣＣＭ及び４〜３２８ＣＣＭのような広い領域まで
得られる。、また、これらの領域に４５ける成膜速度は
、従来の□点ａ１、ｂｌ及びｃｌに比べて１０（８程度
速くすることができる。On the other hand, in the present invention, since the oxygen gas concentration and the target layer 1 are formed by reactive sputtering with the oxygen gas concentration set so that no oxidized layer is formed on the surface of the target layer 1, that is, in an unoxidized layer state, and in C, az
□Area between ab, bl~b) and c2~c5, i.e. [Capacity: 1~88CCM, 2~20CCM, respectively]
3 CCM and wide ranges such as 4-328 CCM are obtained. Furthermore, the film formation rate in these regions can be increased by about 10 (about 8) compared to the conventional □ points a1, bl, and cl.
そして、本発明は透明手段として、成膜後、大気中又は
酸化性雰囲気中で３００〜５００℃にて熱処理し、比抵
抗を低くする手段として、熱処理の降温の際、その冷却
速度を４０〜１ｏＯ℃／分で冷却する。In the present invention, as a transparent means, after the film is formed, heat treatment is performed at 300 to 500°C in the air or an oxidizing atmosphere, and as a means for lowering the specific resistance, the cooling rate is set at 40 to 500° C. Cool at 1oO<0>C/min.
透明導電膜の電気伝導を左右する要因には、例えば酸化
インジウム中に含まれるスズ、酸化スズ中に含まれるア
ンチモンのような不純物の他に、酸素の空格子点の量、
粒子の大きさ及び結晶の配向性など様々なパラメータが
ある。本発明では上記要因のうち、主に酸素の空格子点
の形成に際して、その量を均一かつ最適にして、比抵抗
の低い透明導電膜を形成させる。この酸素の空格子点は
、ある温度で多く生成し、電気伝導に大きく寄与する。Factors that affect the electrical conductivity of transparent conductive films include impurities such as tin contained in indium oxide and antimony contained in tin oxide, as well as the amount of oxygen vacancies,
There are various parameters such as particle size and crystal orientation. In the present invention, among the above-mentioned factors, the amount of oxygen vacancies is uniformly and optimally formed mainly to form a transparent conductive film with low specific resistance. These oxygen vacancies are generated in large numbers at a certain temperature and greatly contribute to electrical conduction.
通常、この温度は３００〜５００℃程度であり、これ以
下の温度では空格子の生成量が少なくなる。Usually, this temperature is about 300 to 500°C, and at temperatures below this, the amount of vacancies produced decreases.
したがって、降温の際、温度を徐々に下げると、空格子
量はその温度における量に追従するために、少なくなる
。Therefore, when the temperature is gradually lowered, the amount of vacancies follows the amount at that temperature, and thus decreases.
一方、本発明によれば、基板と膜が破壊されない程度の
降温で急冷する。すなわち４０〜１００”Ｃ／分の冷却
速度で冷却することにより、徐々に降温するときよりも
、空格子量を多く存在させて、比抵抗を大幅に低減させ
ることができる。On the other hand, according to the present invention, the temperature is rapidly cooled to such an extent that the substrate and film are not destroyed. That is, by cooling at a cooling rate of 40 to 100''C/min, the specific resistance can be significantly reduced by creating a larger amount of vacancies than when the temperature is gradually lowered.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
（実施例１）
ターゲットとしてｔ５ｗｔ％のスズを含むインジウム合
金を使用し、スパッタガスをアルゴン： ７０３ＣＣＭ
と酸素７ｊ［： １６８ ＣＣＩＶＨ： Ｌ／Ｔ、ター
ゲット表面を未酸化層状態にし、チャンバー内圧力を４
ｘ１０ Ｔｏｒｒ 、 スパッタ電流１ｓｐ＝１．５Ａ
にして反応性スパッタリングにより、透明なガラス基４
ｆｆ（ＮＡ−４０：保谷硝子製アルミノシリケートガラ
ス〉上に金属光沢を有するＩｔ！（１１＊厚： １００
ＯＡ ＞を成膜した。成膜後の分光透過率（波長５５０
ｎｌｌｌの光に対する分光透過率。以下同様）は０．５
％であった。次に、成膜したガラス基板を大気中、４０
０℃で１時間熱処理した後、冷却速度２℃／分で冷却し
たときの分光透過率は８５％であり、比抵抗はｌＸ１０
−’Ωａｍであった。(Example 1) An indium alloy containing 5wt% tin was used as a target, and the sputtering gas was argon: 703CCM
and oxygen 7j [: 168 CCIVH: L/T, the target surface is made into an unoxidized layer state, and the chamber pressure is set to 4
x10 Torr, sputtering current 1sp=1.5A
By reactive sputtering, a transparent glass base 4
It! (11*thickness: 100) with metallic luster on ff (NA-40: Hoya Glass aluminosilicate glass)
OA> was deposited. Spectral transmittance after film formation (wavelength 550
Spectral transmittance for nllll light. (same below) is 0.5
%Met. Next, the glass substrate on which the film was formed was placed in the atmosphere for 40 minutes.
After heat treatment at 0°C for 1 hour, the spectral transmittance was 85% when cooling at a cooling rate of 2°C/min, and the specific resistance was 1×10
-'Ωam.
また、成膜したガラス基板を同様に熱処理した後、冷却
速度５０℃／分で１００℃まで降温し、次に、室温にな
るまで放置したときの分光透過率は８５％であり、比抵
抗は５ｘ１０Ωｃｍであった。本例の酸化インジウムを
主体とする膜における酸化スズの含有比率は、酸化スズ
を４ｗｔ％よりも少なくしたり。ｓｏｗｔ％より多くし
た場合、いずれも透過率は変わらないものの、比抵抗が
大きくなり、実用に供しなくなる。したがって、酸化イ
ンジウムを主体とする膜にお番プる酸化スズ含有比率は
４〜５０ｗｔ％の範囲以内が好ましい。Furthermore, after the film-formed glass substrate was heat-treated in the same manner, the temperature was lowered to 100°C at a cooling rate of 50°C/min, and then the spectral transmittance was 85% when it was left to reach room temperature. It was 5x10Ωcm. The content ratio of tin oxide in the film mainly composed of indium oxide in this example is less than 4 wt%. If the amount is more than sowt%, the transmittance remains the same, but the resistivity increases and is no longer practical. Therefore, the content ratio of tin oxide in the film mainly composed of indium oxide is preferably within the range of 4 to 50 wt%.
（実施例２〉
ターゲットとして１０ｗｔ％のアンチモンを含むスズ合
金を使用し、スパッタガスをアルゴン： ６０８ＣＣＭ
と酸素ガス：３５ＳＣＣＭにして、ターゲット表面を未
酸化層状態にし、チャンバー内圧力を５ ｘｉｏ−３−
ｒ ｏｒｒ 、スパッタ電流ｆｓｐ＝１．３Ａにして反
応性スパッタリングにより、透明ガラス基板（ＬＥ〜３
０：保谷硝子製アルミノシリケートガラス）上に金属光
沢を有する膜（膜厚： １ｏｏｏ人）を成膜した。成膜
後の分光透過率は０．６％であった。次に、成膜したガ
ラス基板を大気中、４２０℃で１時間熱処理した後、冷
却速度２℃／分で冷却したときの分光透過率は８３％で
あり、比抵抗は２ｘｌＯ”Ωｃｍであった。本例の酸化
スズを主体とする膜にお【プる酸化アンチモンの含有比
率について、酸化アンチモンを４ｗｔ％より少なくした
り、６０ｗｔ％より多くした場合、いずれも透過率はほ
とんど変わらないが、比抵抗が大きくなり、実用に供し
なくなる。したがって、酸化スズを主体とする膜におけ
る酸化アンチモンの含有比率は４〜６０ｗｔ％の範囲以
内が好ましい。(Example 2) A tin alloy containing 10 wt% antimony was used as a target, and the sputtering gas was argon: 608 CCM
and oxygen gas: 35 SCCM to make the target surface an unoxidized layer, and the chamber pressure was set to 5 xio-3-
A transparent glass substrate (LE~3
A film having metallic luster (thickness: 100 mm) was formed on aluminosilicate glass (manufactured by Hoya Glass Co., Ltd.). The spectral transmittance after film formation was 0.6%. Next, the film-formed glass substrate was heat-treated in the air at 420°C for 1 hour, and then cooled at a cooling rate of 2°C/min. The spectral transmittance was 83% and the specific resistance was 2xlO"Ωcm. Regarding the content ratio of antimony oxide in the film mainly composed of tin oxide in this example, when antimony oxide is made less than 4 wt% or more than 60 wt%, the transmittance remains almost the same. The specific resistance increases, making it unusable for practical use.Therefore, the content ratio of antimony oxide in a film mainly composed of tin oxide is preferably within the range of 4 to 60 wt%.
また、成膜したガラス基板を同様に熱処理した後、冷却
速度５０℃／分で１００℃まで降温し、次に室温まで放
置したときの分光透過率は８３％であり、比抵抗は８ｘ
１０Ωｃｍであった。Furthermore, after the film-formed glass substrate was heat-treated in the same manner, the temperature was lowered to 100°C at a cooling rate of 50°C/min, and then the spectral transmittance was 83% when it was left to stand at room temperature, and the specific resistance was 8x.
It was 10Ωcm.
以上のとおり、本発明によれば、ターゲット表面を未酸
化層状態にしてスパッタリング条件の酸素ガス１ｌｉｔ
１度を設定していることから、そのスパッタリング条件
の制御を容易にして、量産化することができるし、また
、熱処理後に所定の冷却速痘で冷却していることにより
、所望な透過率と比抵抗が得られるから、透明導電膜の
製造方法として非常に有効である。As described above, according to the present invention, 1 liter of oxygen gas under sputtering conditions is used to make the target surface into an unoxidized layer state.
Since the temperature is set at 1 degree, sputtering conditions can be easily controlled and mass production can be carried out.Also, by cooling at a predetermined cooling rate after heat treatment, it is possible to achieve the desired transmittance. Since specific resistance can be obtained, this method is very effective as a method for manufacturing transparent conductive films.
第１図は酸素流量と成膜速度の関係を示す特性図である
。
第 １ 図
７
醸 九 たｉ （ｓｃｃｈ）
手 続 補 正 書 く自発）
（２）く３）
１、事件の表示 昭和５７年特許願第２２６４０５号
２、発明の名称 透明導電膜の製造方法３、補正をす
る者
事件との関係 特許出願人
住所 東京都新宿区西新宿１丁目１３番１２号・１６０
置 ０３（３４８）１２２１ホ ヤ ガラス
名称 株式会社 保 谷 硝 子
明細書の発明の詳細な説明の欄
５、補正の内容
」１
不
看
了
明細書第５頁第８行に１第１図は」とあるを「第１図は
１０ｗｔ％のスズを含むインジウムの合金をターゲット
とづる揚台の」と補正する。
明細書第７頁第８行に［本発明は透明手段として、」と
あるを「本発明は透明にする手段として、」と補正する
。
以上FIG. 1 is a characteristic diagram showing the relationship between oxygen flow rate and film formation rate. Figure 1 7 (scch) Procedural amendment written spontaneously)
(2) 3) 1. Indication of the case Patent Application No. 226405 filed in 1982 2. Title of the invention Method for producing a transparent conductive film 3. Relationship with the person making the amendment Patent applicant address Nishi-Shinjuku, Shinjuku-ku, Tokyo 1-13-12/160
03 (348) 1221 Hoya Glass Name Hoya Glass Co., Ltd. Column 5 of the detailed description of the invention in the specification, Contents of amendments 1 In the 8th line of page 5 of the specification 1 Figure 1 is '' should be corrected to read, ``Figure 1 shows a platform for targeting an indium alloy containing 10 wt% tin.'' On page 7, line 8 of the specification, the phrase "the present invention is used as a transparent means" is amended to read "the present invention is used as a transparent means."that's all
Claims (1)
ッタガスを不活性ガスと酸素ガスを含む混合ガスにし、
前記酸素ガスの濃度によって前記ターゲットの表面を未
酸化層状態に設定して反応性スパッタリングにより、前
記金属材料を透明基板上に成膜した後、大気中又は酸化
性雰囲気中で３００〜５００℃にて熱処理し、次に冷却
することを特徴とする透明導電膜の製造方法。 （２） 熱処理後、冷却速度を４０〜ｂして冷却するこ
とを特徴とする特許請求の範囲第１項記載の透明導電膜
の製造方法。 く３） 透明基板上の膜が４〜５０ｗｔ％の酸化スズを
含む酸化インジウムであることを特徴とする特許請求の
範囲第１項又は第２項記載の透明導電膜の製造方法。 （４） 透明基板上の膜が４〜６０ｗｔ％の酸化アンチ
モンを含む酸化スズであることを特徴とする特許請求の
範囲第１項又は第２項記載の透明導電膜の製造方法。[Claims] (1) Using a metal material for a transparent conductive film as a target, using a sputtering gas as a mixed gas containing an inert gas and an oxygen gas,
The surface of the target is set to an unoxidized layer state depending on the concentration of the oxygen gas, and the metal material is deposited on the transparent substrate by reactive sputtering, and then heated to 300 to 500°C in air or an oxidizing atmosphere. 1. A method for producing a transparent conductive film, which comprises heat-treating and then cooling. (2) The method for manufacturing a transparent conductive film according to claim 1, wherein after the heat treatment, cooling is performed at a cooling rate of 40 to b. 3) The method for producing a transparent conductive film according to claim 1 or 2, wherein the film on the transparent substrate is made of indium oxide containing 4 to 50 wt% of tin oxide. (4) The method for manufacturing a transparent conductive film according to claim 1 or 2, wherein the film on the transparent substrate is tin oxide containing 4 to 60 wt% antimony oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57226405A JPS59117273A (en) | 1982-12-24 | 1982-12-24 | Manufacture of transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57226405A JPS59117273A (en) | 1982-12-24 | 1982-12-24 | Manufacture of transparent conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59117273A true JPS59117273A (en) | 1984-07-06 |
Family
ID=16844598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57226405A Pending JPS59117273A (en) | 1982-12-24 | 1982-12-24 | Manufacture of transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59117273A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6010602A (en) * | 1994-12-27 | 2000-01-04 | Ppg Industries Ohio, Inc. | Annealed low emissivity coating |
| KR101095004B1 (en) | 2008-10-01 | 2011-12-19 | 한국세라믹기술원 | The manufacturing method and Indium Tin OxideITO transparent conductive films deposited on the diffusion barrier layer coated Soda lime glass substrate. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5639003A (en) * | 1979-09-07 | 1981-04-14 | Nippon Kayaku Co Ltd | Method for reducing damage of paddy-rice plant with agricultural chemical |
| JPS56130009A (en) * | 1980-03-17 | 1981-10-12 | Sharp Kk | Method of producing transparent conductive film |
-
1982
- 1982-12-24 JP JP57226405A patent/JPS59117273A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5639003A (en) * | 1979-09-07 | 1981-04-14 | Nippon Kayaku Co Ltd | Method for reducing damage of paddy-rice plant with agricultural chemical |
| JPS56130009A (en) * | 1980-03-17 | 1981-10-12 | Sharp Kk | Method of producing transparent conductive film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6010602A (en) * | 1994-12-27 | 2000-01-04 | Ppg Industries Ohio, Inc. | Annealed low emissivity coating |
| KR101095004B1 (en) | 2008-10-01 | 2011-12-19 | 한국세라믹기술원 | The manufacturing method and Indium Tin OxideITO transparent conductive films deposited on the diffusion barrier layer coated Soda lime glass substrate. |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4087447B2 (en) | Sputtering target and manufacturing method thereof | |
| JP3358893B2 (en) | Transparent conductor containing gallium-indium oxide | |
| JP3970719B2 (en) | Sputtering target based on titanium dioxide | |
| JPS606521B2 (en) | Resistor composition and method for manufacturing the same | |
| JPS63274757A (en) | Bismuth/tin oxide film | |
| JPS62154411A (en) | Transparent conductive film | |
| JPS59117273A (en) | Manufacture of transparent conductive film | |
| JPH02168507A (en) | Fluorine doped tin oxide film and method of reducing resistance thereof | |
| US5473456A (en) | Method for growing transparent conductive gallium-indium-oxide films by sputtering | |
| JPS5998407A (en) | Method of producing transparent conductive film | |
| JPH01145325A (en) | Production of transparent conductive film | |
| JPS6215961B2 (en) | ||
| JPS62227082A (en) | Formation of electrically conductive transparent film | |
| JPS647445B2 (en) | ||
| JP2941086B2 (en) | Transparent electrode | |
| JP3123260B2 (en) | Method for producing transparent conductive film | |
| EP3312313A1 (en) | Lithium niobate single crystal substrate and method for producing same | |
| EP3312315A1 (en) | Lithium niobate single crystal substrate and method for producing same | |
| EP3312312A1 (en) | Lithium niobate single crystal substrate and method for producing same | |
| JP3134405B2 (en) | Method for producing indium oxide / tin oxide sintered body | |
| JP2003081633A (en) | Method for producing resistance-reduced fluorine-doped tin oxide film | |
| JPH0813140A (en) | Indium oxide sputtering target, its production, indium oxide film, and production of indium oxide film | |
| JPS63203757A (en) | Method for annealing tin-added indium oxide film | |
| KR101735999B1 (en) | Double structured tin oxide thin film and fabrication method of the double structured tin oxide thin film | |
| JPS6288216A (en) | Manufacture of transparent conductive film |