JPH04285163A - Ito sputtering target - Google Patents
Ito sputtering targetInfo
- Publication number
- JPH04285163A JPH04285163A JP7057691A JP7057691A JPH04285163A JP H04285163 A JPH04285163 A JP H04285163A JP 7057691 A JP7057691 A JP 7057691A JP 7057691 A JP7057691 A JP 7057691A JP H04285163 A JPH04285163 A JP H04285163A
- Authority
- JP
- Japan
- Prior art keywords
- ito
- density
- target
- sintered
- film
- 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
- 238000005477 sputtering target Methods 0.000 title claims description 6
- 239000002994 raw material Substances 0.000 claims abstract description 13
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 10
- 238000004663 powder metallurgy Methods 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 26
- 230000006866 deterioration Effects 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 42
- 238000005245 sintering Methods 0.000 description 32
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000000843 powder Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 229910003460 diamond Inorganic materials 0.000 description 7
- 239000010432 diamond Substances 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】この発明は、スパッタリングによ
ってＩＴＯ膜（Ｉｎｄｉｕｍ−Ｔｉｎ Ｏｘｉｄｅ膜）
を形成させる際に使用するタ−ゲットに関するもので
ある。[Industrial Application Field] This invention is directed to the production of an ITO film (Indium-Tin Oxide film) by sputtering.
This relates to targets used in forming.
【０００２】0002
【従来技術とその課題】”ＩＴＯ膜” と呼ばれる「ｎ
型導電性の半導体特性」を示す Ｉｎ２Ｏ３ ，ＳｎＯ
２ 酸化物膜は、非常に高い導電性の他に可視光透過性
（透明性）をも有していることから、最近では液晶表示
装置，薄膜エレクトロルミネッセンス表示装置，放射線
検出素子，端末機器の透明タブレット，窓ガラスの結露
防止用発熱膜，帯電防止膜或いは太陽光集熱器用選択透
過膜等、多岐にわたる用途に供されている。そして、こ
のＩＴＯ膜の形成手段としては化合物の熱分解を利用し
たスプレイ法やＣＶＤ法等の化学的成膜法、或いは真空
蒸着法やスパッタリング法等の物理的成膜法等が知られ
ているが、中でも、「大面積で成膜することが可能でか
つ低抵抗膜を再現性良く形成できる」との利点が着目さ
れて“スパッタリング法”の採用が広まってきている。[Prior art and its problems] “n” called “ITO film”
In2O3, SnO exhibiting "type conductive semiconductor properties"
2 Oxide films have not only very high conductivity but also visible light transmission (transparency), so they have recently been used in liquid crystal displays, thin film electroluminescent displays, radiation detection elements, and terminal equipment. It is used in a wide variety of applications, such as transparent tablets, heat-generating films for preventing dew condensation on window glasses, antistatic films, and selectively permeable films for solar collectors. Known methods for forming this ITO film include chemical film-forming methods such as a spray method and CVD method that utilize thermal decomposition of compounds, and physical film-forming methods such as vacuum evaporation method and sputtering method. However, in particular, the adoption of the "sputtering method" has been gaining attention due to its advantages of being able to form a film over a large area and with good reproducibility.
【０００３】ところで、スパッタリング法にてＩＴＯ膜
を形成する場合には酸化インジウムと酸化錫から成るス
パッタリングタ−ゲット（以降“ＩＴＯタ−ゲット”と
略称する）が使用されるが、このＩＴＯタ−ゲットとし
ては、酸化インジウムと酸化錫の粉末混合体、或いはこ
れにド−パントを添加した粉末混合体を常温でプレス成
形し、該成形体を更に大気中にて１２５０〜１６５０℃
で焼結したものが一般に用いられてきた。By the way, when forming an ITO film by sputtering, a sputtering target (hereinafter abbreviated as "ITO target") made of indium oxide and tin oxide is used. As a get, a powder mixture of indium oxide and tin oxide, or a powder mixture with a dopant added thereto, is press-molded at room temperature, and the molded body is further heated at 1250 to 1650°C in the atmosphere.
Sintered materials have generally been used.
【０００４】しかしながら、酸化インジウム粉末や酸化
錫粉末は非常に焼結性の悪い材料であって焼結体密度が
低くなり、そのためか上記方法 （コ−ルドプレス大気
焼結法） で製造されたＩＴＯタ−ゲットには（Ａ）
スパッタリングが進行するにつれて成膜速度｛ＩＴＯ膜
の付着（成長）速度｝が顕著に低下する，（Ｂ） スパ
ッタ時にア−キングと呼ばれる異常放電が発生し、成膜
操作の安定性を害しがちである，（Ｃ） タ−ゲット寿
命が短い，（Ｄ） ＩＴＯ特有の黒色化が顕著で比抵抗
，エッチング特性，透過率等のＩＴＯ膜特性の劣化が顕
著である，（Ｅ） 基板上のゴミ （パ−ティクル）
が増加する，等の不都合が指摘されており、従ってより
一層優れたスパッタリング作業性やＩＴＯ膜品質を確保
できる安価なＩＴＯタ−ゲットが強く望まれていた。However, indium oxide powder and tin oxide powder are materials with very poor sinterability, resulting in a low sintered body density, which may be why ITO produced by the above method (cold press atmospheric sintering method) For the target (A)
As sputtering progresses, the deposition rate {the deposition (growth) rate of the ITO film} decreases markedly. (B) Abnormal discharge called arcing occurs during sputtering, which tends to impair the stability of the deposition operation. Yes, (C) The target life is short, (D) The blackening peculiar to ITO is noticeable, and the ITO film properties such as resistivity, etching characteristics, and transmittance are significantly deteriorated. (E) Dust on the substrate (Particle)
Accordingly, there has been a strong desire for an inexpensive ITO target that can ensure even better sputtering workability and ITO film quality.
【０００５】このため、焼結タ−ゲットを製造するため
の前記一連の工程のうち、 ”粉末原料の成形工程”
にホットプレスを適用した手法（以降“ホットプレス法
”と称する）も実施されるようになったが、この方法で
製造されたＩＴＯタ−ゲットであっても“成膜速度が時
間と共に低下する傾向”や“ア−キングの発生傾向”に
それほど顕著な改善効果は見られないばかりか、更に（
ａ） 設備のイニシャルコストが高騰する上、設備の大
型化も困難となる，（ｂ） 金型等も高価なものを必要
とするので、ランニングコストが高くなる，（ｃ） 一
操業に要する時間が長くなるため量産性に劣る，等の新
たな製造上の問題が生じ、これらが結局はタ−ゲット価
格に影響することから、やはり工業的に十分満足できる
手段とは言い難かった。[0005] For this reason, among the series of steps for producing a sintered target, the "process of forming powder raw materials" is
A method that applies hot pressing (hereinafter referred to as the "hot press method") has also been implemented, but even with ITO targets manufactured using this method, "the film formation rate decreases over time." Not only was there no significant improvement effect on the "trend of arcing" or "tendency of arcing occurrence," but also (
a) The initial cost of the equipment increases and it becomes difficult to increase the size of the equipment, (b) Running costs increase as expensive molds are required, (c) The time required for one operation increases. New manufacturing problems arose, such as poor mass productivity due to the length of the process, and these ultimately affected the target price, so it was still difficult to say that this was an industrially satisfactory means.
【０００６】このようなことから、本発明の目的は、従
来材に指摘された上記問題点が払拭され、スパッタリン
グ作業中に成膜速度が低下したりア−キング発生等によ
る成膜操作の不安定を来たしたりすることがなく、しか
も価格的にも有利なＩＴＯ焼結タ−ゲットを実現するこ
とに置かれた。In view of the above, an object of the present invention is to eliminate the above-mentioned problems pointed out with conventional materials, and to solve problems in film-forming operations such as a decrease in film-forming speed and occurrence of arcing during sputtering. The aim was to realize an ITO sintering target that would not become unstable and would also be advantageous in terms of cost.
【０００７】[0007]
【課題を解決するための手段】本発明者等は上記目的の
達成を目指し、そのためには従来のＩＴＯ焼結タ−ゲッ
トに関するより深い技術的事項の把握が重要であるとの
観点に立って研究を始めたところ、次のような事実が次
々と明らかになったのである。[Means for Solving the Problems] The present inventors aim to achieve the above object, and from the viewpoint that it is important to understand deeper technical matters regarding conventional ITO sintering targets. As I began my research, the following facts became clear one after another.
【０００８】即ち、一般に焼結タ−ゲットはその密度が
性能に大きな影響を与えると言われているため、まず「
コ−ルドプレス大気焼結法」で得られるＩＴＯ焼結タ−
ゲットの密度について検討を加えたところ、このように
製造されたものでは様々な工夫を凝らしたとしても密度
が ４．２〜５．８ ｇ／ｃｍ３ と理論密度の精々６
０〜８０％程度にしか達しないことが確認され、これが
特性値の向上を阻んでいると推定された。これに対して
、「ホットプレス法」で得られるＩＴＯ焼結タ−ゲット
の場合には、その密度が６．０ 〜６．７ｇ／ｃｍ３（
理論密度の８５〜９３％程度）にまで上昇していること
が分かったが、実際には、前述したように上記「ホット
プレス法」で得られるＩＴＯ焼結タ−ゲットのような高
密度品であってもスパッタリング時における成膜操作の
不安定や時間の経過に伴う成膜速度の低下現象が見られ
る。そのため、このような現象の回避にはＩＴＯ焼結タ
−ゲットの密度を更に向上させる必要があると仮定し、
その密度向上手段の確立に取り組んだところ、「ＩＴＯ
焼結タ−ゲットの製造に当って“圧縮成形した酸化物粉
末混合体の焼結”を１気圧以上の高い酸素分圧雰囲気中
で実施すると、 前記酸化物粉末混合体の圧縮成形にコ
−ルドプレス法を適用した場合であっても得られる“Ｉ
ＴＯ焼結タ−ゲット”の密度を７ｇ／ｃｍ３ を超える
程まで（理論密度９７〜９９％程度）に高めることが可
能になる」との新しい知見を得ることができ、この新し
い手法に従って得られたＩＴＯ焼結タ−ゲットの詳細な
特性調査を行った。[0008] In other words, it is generally said that the density of a sintered target has a great effect on its performance.
ITO sintered tar obtained by "cold press atmospheric sintering method"
After considering the density of the get, it was found that even with various efforts, the density of the get produced in this way is 4.2 to 5.8 g/cm3, which is at most 6 of the theoretical density.
It was confirmed that it reached only about 0 to 80%, and it was estimated that this was hindering the improvement of the characteristic values. On the other hand, in the case of an ITO sintered target obtained by the "hot press method", its density is 6.0 to 6.7 g/cm3 (
However, in reality, as mentioned above, high-density products such as the ITO sintered target obtained by the above-mentioned "hot press method" However, instability in the film forming operation during sputtering and a decrease in the film forming rate over time are observed. Therefore, in order to avoid such a phenomenon, it is assumed that it is necessary to further improve the density of the ITO sintered target.
When we worked on establishing a means to improve the density, we found that ``ITO
When producing a sintering target, if "sintering of the compression-molded oxide powder mixture" is carried out in an atmosphere with a high oxygen partial pressure of 1 atm or more, the compression-molding of the oxide powder mixture will be sintered. The “I” obtained even when applying the double press method
We were able to obtain new knowledge that it is possible to increase the density of the TO sintered target to over 7 g/cm3 (approximately 97 to 99% of the theoretical density). A detailed investigation of the characteristics of the ITO sintered target was conducted.
【０００９】この結果、上記「酸素雰囲気中焼結ＩＴＯ
タ−ゲット」は ”タ−ゲット寿命”，”スパッタリン
グにより得られるＩＴＯ膜の性能” 等の何れにおいて
も従来材を凌駕するばかりか、“成膜速度”， ”膜特
性の劣化の改善” 並びに“成膜操作安定性”の面でも
飛躍的な向上を遂げていることが確認された。しかも、
これらの優れた特性が、従来の「ホットプレス法」で得
られるＩＴＯ焼結タ−ゲットよりも低い密度となってい
る「酸素雰囲気中焼結ＩＴＯタ−ゲット」にも認められ
たのである。As a result, the above-mentioned ``ITO sintered in an oxygen atmosphere''
"Target" not only surpasses conventional materials in terms of "target life" and "performance of ITO films obtained by sputtering," but also improves "film formation speed,""improves deterioration of film properties," and It was confirmed that a dramatic improvement was also achieved in terms of "film-forming operation stability." Moreover,
These excellent properties were also found in the ``ITO target sintered in an oxygen atmosphere,'' which has a lower density than the ITO sintered target obtained by the conventional ``hot press method.''
【００１０】そこで、様々な角度からその理由を究明し
たところ次の知見を得るに至った。
ｉ） ＩＴＯ焼結タ−ゲットの成膜速度安定性や成膜操
作の安定性等にはその密度が深く係わっていることは勿
論であるが、バルク抵抗値も密接に関連しており、密度
とバルク抵抗値が特定の領域にあるＩＴＯ焼結タ−ゲッ
トでは「スパッタの進行に伴って成膜速度が顕著に低下
する現象」が見られないばかりか、スパッタ時における
ア−キングの発生が少なくなって成膜操作の安定性が格
段に向上し、高性能のＩＴＯ膜を能率良く安定して形成
することが可能である，
ｉｉ） 上記“密度とバルク抵抗値が特定の領域にあ
るＩＴＯ焼結タ−ゲット”は従来の「コ−ルドプレス大
気焼結法」や「ホットプレス法」では実現が困難である
が、前述した「酸素雰囲気中焼結法」によれば安定して
製造することが可能であって、しかも製造コストを安く
抑えることができる。[0010] When we investigated the reason from various angles, we came to the following findings. i) It goes without saying that the film-forming rate stability and stability of the film-forming operation of the ITO sintered target are deeply related to its density, but the bulk resistance value is also closely related. For ITO sintered targets whose bulk resistance values are in a specific range, not only is there no phenomenon in which the film formation rate decreases significantly as sputtering progresses, but arcing also occurs during sputtering. ii) ITO whose density and bulk resistance value are in a specific range It is difficult to produce a sintered target using the conventional ``cold press atmospheric sintering method'' or ``hot press method,'' but it can be stably produced using the ``oxygen atmosphere sintering method'' mentioned above. In addition, manufacturing costs can be kept low.
【００１１】本発明は、上記知見事項等に基づいて完成
されたものであり、
「密度Ｄ（ｇ／ｃｍ３）とバルク抵抗値ρ（ｍΩｃｍ）
がａ） ５．５０ ≦ Ｄ ≦ ７．２３ ，
ｂ） −０．０６７６Ｄ＋０．８８７ ≧
ρ ≧ −０．０７６１Ｄ＋０．６６６ ，なる２
つの式を同時に満たして成るところの“酸化インジウム
と酸化錫を主成分とした原料から粉末冶金法にて製造さ
れたＩＴＯタ−ゲット”を提供し、 高い成膜速度が確
保できることは勿論、 優れた成膜速度安定性，膜特性
の安定性，成膜操作安定性を実現できるようにした点」
に大きな特徴を有している。[0011] The present invention was completed based on the above-mentioned findings, etc.
a) 5.50 ≦ D ≦ 7.23,
b) −0.0676D+0.887≧
ρ ≧ −0.0761D+0.666, becomes 2
We provide an "ITO target manufactured by powder metallurgy from raw materials mainly composed of indium oxide and tin oxide" that satisfies the following formulas at the same time.It not only ensures a high film formation rate but also has excellent The major feature of this method is that it has been able to achieve stable film-forming speed, stable film properties, and stable film-forming operations.
【００１２】なお、本発明においてＩＴＯ焼結タ−ゲッ
トの“密度Ｄ”及び“バルク抵抗値ρ”を前記の如き範
囲に限定した理由は次の通りである。ＩＴＯ焼結タ−ゲ
ットの密度Ｄはスパッタ時の成膜速度，成膜速度安定性
，バルク抵抗値と密接に関連するが、該密度が５．５０
ｇ／ｃｍ３ を下回ると特に成膜速度安定性が損なわれ
てスパッタの進行に伴い成膜速度が低下する現象が目立
つようになる。一方、７．２３ｇ／ｃｍ３ を上回る領
域にまでＩＴＯ焼結タ−ゲットの密度を上昇させること
は「酸素雰囲気中焼結法」によっても非常に困難で、コ
スト的な不利を招くことになる。従って、ＩＴＯ焼結タ
−ゲットの密度は５．５０〜７．２３ｇ／ｃｍ３ と定
めたが、実際的には６．７０ｇ／ｃｍ３ を超え７．２
３ｇ／ｃｍ３ 以下の範囲が好ましい領域と言える。The reason why the "density D" and "bulk resistance value ρ" of the ITO sintered target are limited to the above ranges in the present invention is as follows. The density D of the ITO sintered target is closely related to the film formation rate during sputtering, film formation rate stability, and bulk resistance value.
If it is less than g/cm3, the stability of the film formation rate is particularly impaired, and the phenomenon that the film formation rate decreases as sputtering progresses becomes noticeable. On the other hand, it is very difficult to increase the density of the ITO sintering target to a region exceeding 7.23 g/cm3 even by the "oxygen atmosphere sintering method", which results in a cost disadvantage. Therefore, the density of the ITO sintered target was determined to be 5.50 to 7.23 g/cm3, but in reality it exceeds 6.70 g/cm3 and is 7.2 g/cm3.
A range of 3 g/cm 3 or less can be said to be a preferable range.
【００１３】ＩＴＯ焼結タ−ゲットのバルク抵抗値ρは
、その密度Ｄに大きく依存する傾向があり、例えば図１
に示されるように密度が高くなると急激に低下する傾向
を示す。そして、このバルク抵抗値が低い程スパッタ時
におけるア−キングの発生が少ないので好ましいが、密
度５．５０〜７．２３ｇ／ｃｍ３ の領域でρ ＜
−０．０７６１Ｄ＋０．６６６を達成することは「酸
素雰囲気中焼結法」によっても非常に困難である。一方
、ＩＴＯ焼結タ−ゲットのバルク抵抗値ρが
ρ ＞ −０．０６７６Ｄ＋０．８８７の領域にな
るとスパッタ時におけるア−キングの発生が多くなって
成膜操作の安定性が損なわれるばかりか、成膜速度も不
安定となってスパッタの進行に伴い成膜速度が低下する
現象が著しくなる。従って、ＩＴＯ焼結タ−ゲットのバ
ルク抵抗値ρは
−０．０６７６Ｄ＋０．８８７ ≧ ρ ≧−０．
０７６１Ｄ＋０．６６６の範囲と定めたが、出来れば
−０．０６７６Ｄ＋０．６８７ ≧ ρ ≧−０．
０７６１Ｄ＋０．６６６の範囲に調整するのが好ましい
。The bulk resistance value ρ of an ITO sintered target tends to depend largely on its density D; for example, as shown in FIG.
As shown in , it shows a tendency to decrease rapidly as the density increases. The lower the bulk resistance value is, the less arcing occurs during sputtering, which is preferable, but in the density range of 5.50 to 7.23 g/cm3, ρ <
It is very difficult to achieve -0.0761D+0.666 even by the "oxygen atmosphere sintering method". On the other hand, if the bulk resistance value ρ of the ITO sintered target falls within the range of ρ > -0.0676D+0.887, arcing will occur more frequently during sputtering, which will not only impair the stability of the film-forming operation. The film formation rate also becomes unstable, and the phenomenon that the film formation rate decreases becomes remarkable as sputtering progresses. Therefore, the bulk resistance value ρ of the ITO sintered target is -0.0676D+0.887 ≧ ρ ≧ -0.
The range is set as 0761D+0.666, but preferably -0.0676D+0.687 ≧ ρ ≧ -0.
It is preferable to adjust to a range of 0.0761D+0.666.
【００１４】なお、本発明に係わるＩＴＯ焼結タ−ゲッ
トの密度やバルク抵抗値の調整は、原料粉をプレス成形
する際のプレス圧，焼結時の雰囲気（酸素分圧），焼結
温度等を調節することによって可能である。[0014] The density and bulk resistance of the ITO sintering target according to the present invention can be adjusted by adjusting the press pressure when press-molding the raw material powder, the atmosphere during sintering (oxygen partial pressure), and the sintering temperature. It is possible by adjusting etc.
【００１５】さて、先にも述べたように、本発明に係わ
るＩＴＯ焼結タ−ゲットは、常法の如く酸化インジウム
と酸化錫を主成分とする粉末混合体をプレス成形し焼結
してＩＴＯタ−ゲットを製造する際に、前記焼結を“１
気圧（絶対圧）以上に加圧された純酸素ガス雰囲気”，
”Ｏ２ 分圧が１気圧以上である混合ガス雰囲気”等
の加圧酸素雰囲気中で行うことにより得られるものであ
るが、焼結工程を加圧酸素雰囲気とすることで性能の良
好な上記製品が得られる理由は、現在のところ未だ明確
ではない。しかし、「焼結をＮ２ やＡｒの如き不活性
なガスの雰囲気中で実施した場合にはＩＴＯの分解が生
じて焼結体の密度や性能が低下する」との事実と、大気
中であってもＩＴＯは高温に加熱されると酸素を解離し
易い性質を有することから、焼結時に酸素加圧すること
で高温加熱によるＩＴＯの解離が効果的に防止されると
共に、酸素が焼結助剤的な働きをして密度向上やバルク
抵抗の低下等に寄与しているのではないかと推測される
。また、加圧酸素雰囲気中での焼結温度は従来の大気中
焼結の場合と同様に１６００〜１７００℃程度が適当で
あり、焼結時間は３時間以上とするのが望ましい（焼結
時間は長いほど好結果が得られる）。Now, as mentioned above, the ITO sintering target according to the present invention is produced by press-molding and sintering a powder mixture containing indium oxide and tin oxide as main components in the usual manner. When manufacturing an ITO target, the sintering process is
Pure oxygen gas atmosphere pressurized above atmospheric pressure (absolute pressure)”
This product can be obtained by performing the sintering process in a pressurized oxygen atmosphere such as a mixed gas atmosphere with an O2 partial pressure of 1 atm or more. The reason why this is obtained is currently not clear. However, the fact that ``if sintering is performed in an atmosphere of an inert gas such as N2 or Ar, decomposition of ITO will occur, reducing the density and performance of the sintered body,'' and However, ITO has the property of easily dissociating oxygen when heated to high temperatures, so by pressurizing oxygen during sintering, dissociation of ITO due to high temperature heating is effectively prevented, and oxygen becomes a sintering aid. It is speculated that this may contribute to an increase in density and a decrease in bulk resistance. In addition, the appropriate sintering temperature in a pressurized oxygen atmosphere is about 1,600 to 1,700°C, as in the case of conventional atmospheric sintering, and the sintering time is preferably 3 hours or more (sintering time (The longer the length, the better the results).
【００１６】続いて、本発明を実施例により比較例と対
比しながら更に具体的に説明する。[0016] Next, the present invention will be explained in more detail by examples and in comparison with comparative examples.
【実施例】〔実施例１〕まず、平均粒径が２μｍの酸化
インジウム粉と同じ粒度の酸化錫粉を重量比で９０：１
０となるように均一に混合し、これに成形用のバインダ
−を加えてから、コ−ルドプレスの場合は金型（１６５
Ｗ ×５２０Ｌ ）へ、ホットプレスの場合はグラファ
イト型（２３０φ）へそれぞれ均一に充填した。続いて
、次の各工程に従い 「本発明品１」， 「本発明品２
」， 「比較品：コ−ルドプレス大気焼結品」 及び
「比較品：ホットプレス品」 なるＩＴＯ焼結タ−ゲッ
トを得た。[Example] [Example 1] First, indium oxide powder with an average particle size of 2 μm and tin oxide powder with the same particle size were mixed in a weight ratio of 90:1.
Mix uniformly so that
W × 520L), and in the case of hot pressing, a graphite mold (230φ) was filled uniformly. Next, according to each of the following steps, "Product 1 of the present invention" and "Product 2 of the present invention"
”, “Comparative product: cold press atmospheric sintered product” and
An ITO sintered target called "Comparative product: hot pressed product" was obtained.
【００１７】本発明品１：金型に充填した原料混合粉を
油圧プレスにて７５０ｋｇ／ｃｍ２の圧力で加圧してか
らこれを８０℃に加熱してバインダ−中の水分を蒸発さ
せて乾燥し、次いで加圧焼結炉により１気圧（絶対圧）
の純酸素ガス雰囲気中にて１６５０℃で９時間焼結する
。次に、得られた焼結体の表面を平面研削盤で削り、更
に側辺をダイヤモンドカッタ−で切断してタ−ゲット製
品とした。得られたＩＴＯ焼結タ−ゲット製品の密度は
６．３５ｇ／ｃｍ３ ，バルク抵抗値は０．２２ ｍΩ
ｃｍであった。Invention product 1: The raw material mixed powder filled in a mold is pressurized with a pressure of 750 kg/cm2 using a hydraulic press, and then heated to 80°C to evaporate the moisture in the binder and dry it. , then 1 atm (absolute pressure) in a pressure sintering furnace.
Sintering was performed at 1650° C. for 9 hours in a pure oxygen gas atmosphere. Next, the surface of the obtained sintered body was ground with a surface grinder, and the sides were cut with a diamond cutter to obtain a target product. The density of the obtained ITO sintered target product was 6.35 g/cm3, and the bulk resistance value was 0.22 mΩ.
It was cm.
【００１８】本発明品２：金型に充填した原料混合粉を
油圧プレスにて１０００ｋｇ／ｃｍ２の圧力で加圧して
からこれを８０℃に加熱してバインダ−中の水分を蒸発
させて乾燥し、次いで加圧焼結炉により ４．５気圧（
絶対圧）の純酸素ガス雰囲気中にて１６５０℃で９時間
焼結する。
次に、得られた焼結体の表面を平面研削盤で削り、更に
側辺をダイヤモンドカッタ−で切断してタ−ゲット製品
とした。得られたＩＴＯ焼結タ−ゲット製品の密度は７
．２３ｇ／ｃｍ３ ，バルク抵抗値は０．１２ ｍΩｃ
ｍであった。Invention product 2: The raw material mixed powder filled in the mold is pressurized with a pressure of 1000 kg/cm2 using a hydraulic press, and then heated to 80°C to evaporate the moisture in the binder and dry it. , then in a pressure sintering furnace at 4.5 atm (
Sintering is performed at 1650° C. for 9 hours in a pure oxygen gas atmosphere (absolute pressure). Next, the surface of the obtained sintered body was ground with a surface grinder, and the sides were cut with a diamond cutter to obtain a target product. The density of the obtained ITO sintered target product is 7
．． 23g/cm3, bulk resistance value is 0.12 mΩc
It was m.
【００１９】比較品（コ−ルドプレス大気焼結品）：金
型に充填した原料混合粉を油圧プレスにて１０００ｋｇ
／ｃｍ２の圧力で加圧してからこれを８０℃に加熱して
バインダ−中の水分を蒸発させて乾燥し、次いで大気中
にて１６５０℃で９時間焼結する。次に、得られた焼結
体の表面を平面研削盤で削り、側辺をダイヤモンドカッ
タ−で切断してタ−ゲット製品とした。得られたＩＴＯ
焼結タ−ゲット製品の密度は５．８１ｇ／ｃｍ３ ，バ
ルク抵抗値は０．７５ ｍΩｃｍであった。[0019] Comparative product (cold press atmospheric sintered product): 1000 kg of raw material mixed powder filled in a mold was pressed using a hydraulic press.
The binder was pressurized at a pressure of /cm2, then heated to 80°C to evaporate the moisture in the binder and dried, and then sintered in the air at 1650°C for 9 hours. Next, the surface of the obtained sintered body was ground with a surface grinder, and the sides were cut with a diamond cutter to obtain a target product. Obtained ITO
The density of the sintered target product was 5.81 g/cm3, and the bulk resistance value was 0.75 mΩcm.
【００２０】比較品（ホットプレス品）：グラファイト
型へ８０℃に加熱し乾燥後冷却した原料混合粉を充填し
、Ａｒ雰囲気中にて加圧力：３００ｋｇ／ｃｍ２，加熱
温度：９００℃，加圧加熱時間：１時間なる条件でホッ
トプレスして焼結を行った。次に、得られた焼結体の表
面を平面研削盤で削り、更に側辺をダイヤモンドカッタ
−で切断してタ−ゲット製品とした。得られたＩＴＯ焼
結タ−ゲット製品の密度は６．４２ｇ／ｃｍ３ ，バル
ク抵抗値は０．６０ｍΩｃｍであった。[0020] Comparative product (hot pressed product): A graphite mold was filled with raw material mixed powder heated to 80°C, dried and cooled, and in an Ar atmosphere, pressure: 300 kg/cm2, heating temperature: 900°C, pressure Sintering was performed by hot pressing under conditions of heating time: 1 hour. Next, the surface of the obtained sintered body was ground with a surface grinder, and the sides were cut with a diamond cutter to obtain a target product. The density of the obtained ITO sintered target product was 6.42 g/cm3, and the bulk resistance value was 0.60 mΩcm.
【００２１】〔実施例２〕平均粒径が２μｍの酸化イン
ジウム粉と同じ粒度の酸化錫粉を重量比で９０：１０と
なるように均一に混合し、これに成形用のバインダ−を
加えてから、金型（１６５Ｗ ×５２０Ｌ ）へ均一に
充填した。続いて、次の各工程に従い 「本発明品」，
「比較品：コ−ルドプレス大気焼結品」 及び 「比
較品：ホットプレス品」 なるＩＴＯ焼結タ−ゲットを
得た。[Example 2] Indium oxide powder with an average particle size of 2 μm and tin oxide powder with the same particle size were mixed uniformly at a weight ratio of 90:10, and a binder for molding was added to this. Then, it was uniformly filled into a mold (165W x 520L). Next, according to the following steps, the "product of the present invention",
ITO sintered targets called "Comparative product: cold press atmospheric sintered product" and "Comparative product: hot press product" were obtained.
【００２２】本発明品：金型に充填した原料混合粉を油
圧プレスにて７５０ｋｇ／ｃｍ２の圧力で加圧してから
これを８０℃に加熱してバインダ−中の水分を蒸発させ
て乾燥し、次いで加圧焼結炉により ４．５気圧（絶対
圧）の純酸素ガス雰囲気中にて１６５０℃で９時間焼結
する。次に、得られた焼結体の表面を平面研削盤で削り
、更に側辺をダイヤモンドカッタ−で切断してタ−ゲッ
ト製品とした。得られたＩＴＯ焼結タ−ゲット製品の密
度は６．９０ｇ／ｃｍ３ ，バルク抵抗値は０．１５
ｍΩｃｍであった。Product of the present invention: The raw material mixed powder filled in a mold is pressurized with a pressure of 750 kg/cm2 using a hydraulic press, and then heated to 80° C. to evaporate the moisture in the binder and dry it. Next, it is sintered in a pressure sintering furnace at 1650° C. for 9 hours in a pure oxygen gas atmosphere of 4.5 atmospheres (absolute pressure). Next, the surface of the obtained sintered body was ground with a surface grinder, and the sides were cut with a diamond cutter to obtain a target product. The density of the obtained ITO sintered target product was 6.90 g/cm3, and the bulk resistance value was 0.15.
It was mΩcm.
【００２３】比較品（コ−ルドプレス大気焼結品）：金
型に充填した原料混合粉を油圧プレスにて７５０ｋｇ／
ｃｍ２の圧力で加圧してからこれを８０℃に加熱してバ
インダ−中の水分を蒸発させて乾燥し、次いで大気中に
て１６５０℃で９時間焼結する。次に、得られた焼結体
の表面を平面研削盤で削り、側辺をダイヤモンドカッタ
−で切断してタ−ゲット製品とした。得られたＩＴＯ焼
結タ−ゲット製品の密度は５．５４ｇ／ｃｍ３ ，バル
ク抵抗値は０．８４ ｍΩｃｍであった。[0023] Comparative product (cold press atmospheric sintered product): 750 kg/kg of raw material mixed powder filled in a mold was pressed using a hydraulic press.
After pressurizing at a pressure of cm 2 , this is heated to 80° C. to evaporate the moisture in the binder and dried, and then sintered at 1650° C. in the air for 9 hours. Next, the surface of the obtained sintered body was ground with a surface grinder, and the sides were cut with a diamond cutter to obtain a target product. The density of the obtained ITO sintered target product was 5.54 g/cm3, and the bulk resistance value was 0.84 mΩcm.
【００２４】比較品（ホットプレス品）：グラファイト
型へ８０℃に加熱乾燥後冷却した原料混合粉を充填し、
Ａｒ雰囲気中にて加圧力：３００ｋｇ／ｃｍ２，加熱温
度：９００℃，加圧加熱時間：１時間なる条件でホット
プレスして焼結を行った。次に、得られた焼結体の表面
を平面研削盤で削り、更に側辺をダイヤモンドカッタ−
で切断してタ−ゲット製品とした。このようにして得ら
れたＩＴＯ焼結タ−ゲット製品の密度は６．１０ｇ／ｃ
ｍ３ ，バルク抵抗値は０．７７ ｍΩｃｍであった。[0024] Comparative product (hot pressed product): Fill a graphite mold with a raw material mixture powder that has been heated and dried at 80°C and then cooled.
Sintering was performed by hot pressing in an Ar atmosphere under the following conditions: pressurizing force: 300 kg/cm2, heating temperature: 900° C., pressurizing heating time: 1 hour. Next, the surface of the obtained sintered body was ground with a surface grinder, and the sides were cut with a diamond cutter.
It was cut into target products. The density of the ITO sintered target product thus obtained was 6.10 g/c.
m3, and the bulk resistance value was 0.77 mΩcm.
【００２５】なお、このようにして得られた各ＩＴＯ焼
結タ−ゲットの“密度”及び“バルク抵抗値”をグラフ
上に表わすと図２のようになる。Incidentally, the "density" and "bulk resistance value" of each ITO sintered target thus obtained are shown on a graph as shown in FIG.
【００２６】そして、上記各ＩＴＯ焼結タ−ゲットを用
いてスパッタリング試験を行ったところ、 「本発明品
１」 及び 「本発明品２」 の場合には安定した操業
下で性能の良好な（低抵抗の）透明ＩＴＯ膜が形成され
たのに対して、 「比較品」 を用いた場合には、何れ
もスパッタの進行につれて成膜速度が著しく低下する現
象が見られたばかりか、スパッタ時にア−キングが頻発
して操業が不安定化する傾向が認められた。[0026] Sputtering tests were conducted using each of the above ITO sintered targets, and it was found that "Product 1 of the present invention" and "Product 2 of the present invention" had good performance under stable operation. A transparent ITO film (with low resistance) was formed, whereas when using the ``comparative product,'' not only did the film formation rate drop significantly as sputtering progressed, but also the film formation rate decreased significantly as sputtering progressed. - There was a tendency for kings to occur frequently and operations to become unstable.
【００２７】次に、上記各ＩＴＯ焼結タ−ゲットを用い
ると共に下記条件でスパッタリング試験を行い、各々の
スパッタ時における成膜速度（付着速度）及び膜の比抵
抗の動向を調査したところ、図３及び図４に示す結果が
得られた。
イ） 成膜条件１（バッチ式マシン使用）…スパッタパ
ワ−： ２．３Ｗ／ｃｍ２，ガス圧： ５×１０−３Ｔ
ｏｒｒ，
Ｏ２ 組成：１％。
ロ） 成膜条件２（インライン式マシン使用）…スパッ
タパワ−： １．２Ｗ／ｃｍ２，ガス圧： ５×１０−
３Ｔｏｒｒ，
Ｏ２ 組成：１％。
図３及び図４に示される結果からも、「本発明品」を使
用した場合にはスパッタを長時間継続しても成膜速度或
いは膜の比抵抗がほぼ一定であるのに対して、「比較品
」を用いた場合には、スパッタの進行に伴って著しい成
膜速度の低下或いは膜の比抵抗の増大が起きることが明
らかである。Next, a sputtering test was conducted using each of the above ITO sintered targets and under the following conditions, and trends in the film formation rate (adhesion speed) and specific resistance of the film during each sputtering process were investigated. The results shown in Figures 3 and 4 were obtained. b) Film forming conditions 1 (using batch type machine)...Sputter power: 2.3 W/cm2, gas pressure: 5 x 10-3T
orr, O2 composition: 1%. b) Film forming conditions 2 (using an in-line machine)...Sputter power: 1.2 W/cm2, gas pressure: 5 x 10-
3 Torr, O2 composition: 1%. From the results shown in FIGS. 3 and 4, it is clear that when the "product of the present invention" is used, the film formation rate or specific resistance of the film remains almost constant even if sputtering is continued for a long time, whereas " It is clear that when the "comparative product" is used, as sputtering progresses, the film formation rate decreases significantly or the specific resistance of the film increases.
【００２８】[0028]
【効果の総括】以上に説明した如く、この発明によれば
、スパッタ性能の優れた価格の安いＩＴＯ焼結タ−ゲッ
トを提供することが可能となり、該タ−ゲットを用いれ
ば基板上に極めて抵抗値の低いＩＴＯ透明導電膜を高能
率かつ安定に形成することができ、これを電極とする太
陽電池や画像ディスプレイ装置等の性能向上，消費電力
低減等が達成されるなど、産業上極めて有用な効果がも
たらされる。[Summary of Effects] As explained above, according to the present invention, it is possible to provide an inexpensive ITO sintered target with excellent sputtering performance. ITO transparent conductive films with low resistance can be formed efficiently and stably, and are extremely useful in industry, as they can improve the performance and reduce power consumption of solar cells and image display devices that use them as electrodes. effect is brought about.
【図１】ＩＴＯ焼結タ−ゲットの密度に対するバルク抵
抗の変化傾向を示すグラフである。FIG. 1 is a graph showing the tendency of change in bulk resistance with respect to density of an ITO sintered target.
【図２】実施例と比較例に係わるＩＴＯ焼結タ−ゲット
の密度及びバルク抵抗を示したグラフである。FIG. 2 is a graph showing the density and bulk resistance of ITO sintered targets in Examples and Comparative Examples.
【図３】実施例と比較例に係わるＩＴＯ焼結タ−ゲット
における、スパッタ時の成膜速度（付着速度）動向を示
したグラフである。FIG. 3 is a graph showing trends in film formation rate (deposition rate) during sputtering in ITO sintered targets according to Examples and Comparative Examples.
【図４】実施例と比較例に係わるＩＴＯ焼結タ−ゲット
から成膜されたＩＴＯ膜の抵抗率の動向を示したグラフ
である。FIG. 4 is a graph showing trends in resistivity of ITO films formed from ITO sintered targets according to Examples and Comparative Examples.
Claims (2)
た原料から粉末冶金法にて製造されたＩＴＯスパッタリ
ングタ−ゲットであって、密度Ｄ（ｇ／ｃｍ３）とバル
ク抵抗値ρ（ｍΩｃｍ）が下記２つの式を同時に満たし
て成るＩＴＯスパッタリングタ−ゲット。 ａ） ５．５０ ≦ Ｄ ≦ ７．２３ ，
ｂ） −０．０６７６Ｄ＋０．８８７ ≧
ρ ≧ −０．０７６１Ｄ＋０．６６６ 。Claim 1: An ITO sputtering target manufactured by powder metallurgy from raw materials containing indium oxide and tin oxide as main components, which has a density D (g/cm3) and a bulk resistance value ρ (mΩcm). An ITO sputtering target that simultaneously satisfies the following two formulas. a) 5.50≦D≦7.23,
b) −0.0676D+0.887≧
ρ≧−0.0761D+0.666.
た原料から粉末冶金法にて製造されたＩＴＯスパッタリ
ングタ−ゲットであって、密度Ｄ（ｇ／ｃｍ３）とバル
ク抵抗値ρ（ｍΩｃｍ）が下記２つの式を同時に満たし
て成るＩＴＯスパッタリングタ−ゲット。 ａ） ６．７０ ＜ Ｄ ≦ ７．２３ ，
ｂ） −０．０６７６Ｄ＋０．６８７ ≧
ρ ≧−０．０７６１Ｄ＋０．６６６ 。2. An ITO sputtering target manufactured by powder metallurgy from raw materials containing indium oxide and tin oxide as main components, which has a density D (g/cm3) and a bulk resistance value ρ (mΩcm). An ITO sputtering target that simultaneously satisfies the following two formulas. a) 6.70 < D ≦ 7.23,
b) −0.0676D+0.687 ≧
ρ≧−0.0761D+0.666.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7057691A JPH04285163A (en) | 1991-03-11 | 1991-03-11 | Ito sputtering target |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7057691A JPH04285163A (en) | 1991-03-11 | 1991-03-11 | Ito sputtering target |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04285163A true JPH04285163A (en) | 1992-10-09 |
Family
ID=13435519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7057691A Pending JPH04285163A (en) | 1991-03-11 | 1991-03-11 | Ito sputtering target |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04285163A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6340756A (en) * | 1986-08-07 | 1988-02-22 | 旭硝子株式会社 | Indium oxide sintered body for tin-containing physical vapor deposition |
| JPH02297812A (en) * | 1989-02-28 | 1990-12-10 | Tosoh Corp | Sintered body of oxide, manufacture thereof, and target using same |
| JPH0344464A (en) * | 1989-07-13 | 1991-02-26 | Nippon Mining Co Ltd | Sputtering target for electrically conductive transparent ito film |
-
1991
- 1991-03-11 JP JP7057691A patent/JPH04285163A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6340756A (en) * | 1986-08-07 | 1988-02-22 | 旭硝子株式会社 | Indium oxide sintered body for tin-containing physical vapor deposition |
| JPH02297812A (en) * | 1989-02-28 | 1990-12-10 | Tosoh Corp | Sintered body of oxide, manufacture thereof, and target using same |
| JPH0344464A (en) * | 1989-07-13 | 1991-02-26 | Nippon Mining Co Ltd | Sputtering target for electrically conductive transparent ito film |
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