JP4481239B2 - Sputtering target for high resistance transparent conductive film, high resistance transparent conductive film and method for producing the same - Google Patents
Sputtering target for high resistance transparent conductive film, high resistance transparent conductive film and method for producing the same Download PDFInfo
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- 238000005477 sputtering target Methods 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000002834 transmittance Methods 0.000 claims description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 32
- 229910052738 indium Inorganic materials 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 229910003437 indium oxide Inorganic materials 0.000 claims description 17
- 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 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 11
- 229910001887 tin oxide Inorganic materials 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 98
- 239000000843 powder Substances 0.000 description 65
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 51
- 229910004298 SiO 2 Inorganic materials 0.000 description 50
- 239000012535 impurity Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 34
- 238000004458 analytical method Methods 0.000 description 33
- 229910006404 SnO 2 Inorganic materials 0.000 description 28
- 238000000034 method Methods 0.000 description 24
- 238000000465 moulding Methods 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000001755 magnetron sputter deposition Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- AZWHFTKIBIQKCA-UHFFFAOYSA-N [Sn+2]=O.[O-2].[In+3] Chemical compound [Sn+2]=O.[O-2].[In+3] AZWHFTKIBIQKCA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
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- 230000002687 intercalation Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Description
本発明は、抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗透明導電膜を形成するときに用いられる高抵抗透明導電膜用スパッタリングターゲット及びそれを用いた高抵抗透明導電膜並びにその製造方法に関する。 The present invention relates to a sputtering target for a high resistance transparent conductive film used when forming a high resistance transparent conductive film having a resistivity of 0.9 × 10 −3 to 10 × 10 −3 Ω · cm, and a high The present invention relates to a resistive transparent conductive film and a method for manufacturing the same.
酸化インジウム−酸化錫（Ｉｎ２Ｏ３−ＳｎＯ２の複合酸化物、以下、「ＩＴＯ」という）膜は、可視光透過性が高く、かつ導電性が高いので透明導電膜として液晶表示装置やガラスの結露防止用発熱膜、赤外線反射膜等に幅広く用いられている。 An indium oxide-tin oxide (In 2 O 3 —SnO 2 composite oxide, hereinafter referred to as “ITO”) film has high visible light permeability and high conductivity, so that it is a liquid crystal display device or glass as a transparent conductive film. It is widely used for heat generation films for preventing condensation, infrared reflection films, and the like.
例えば、フラットパネルディスプレイ（ＦＰＤ）に使われる透明導電膜は、低抵抗（抵抗率２×１０−４Ω・ｃｍ程度）のものが選択される。 For example, a transparent conductive film used for a flat panel display (FPD) is selected to have a low resistance (resistivity of about 2 × 10 −4 Ω · cm).
一方、このようなＦＰＤ等に取り付けて使われる抵抗式タッチパネル用透明導電膜は、その原理上、高抵抗なもの（シート抵抗７００〜１０００Ω程度）が要求特性として求められている。 On the other hand, a transparent conductive film for a resistive touch panel that is used by being attached to such an FPD or the like is required to have a high resistance (sheet resistance of about 700 to 1000Ω) as a required characteristic.
しかしながら、従来、ＦＰＤ用に使用されているＩＴＯを用いると、非常に薄い膜としなければならず、タッチパネルとしての強度が確保できないという問題がある。 However, when ITO conventionally used for FPD is used, it has to be a very thin film, and there is a problem that strength as a touch panel cannot be secured.
このような状況下、酸化インジウムを主成分として、これに酸化スズと酸化ケイ素または／および酸化アルミニウムとがドーピングされた透明導電膜が、高抵抗でかつ良好な透明性を有するものとして提案されている（特許文献１参照）。 Under such circumstances, a transparent conductive film mainly composed of indium oxide and doped with tin oxide and silicon oxide or / and aluminum oxide has been proposed as having high resistance and good transparency. (See Patent Document 1).
しかしながら、かかる公報の実施例によると、透明導電膜を形成するスパッタリングターゲットは焼結体でなく圧粉体であり、高周波マグネトロンスパッタリング装置にて透明導電膜を形成している。すなわち、スパッタリングターゲットが高抵抗でＤＣマグネトロンが使用できないものである。また、形成された透明導電膜は、抵抗率が１．７×１０−３〜３．４×１０−３Ω・ｃｍと高抵抗ではあるが、光透過率が８２〜８３％と非常に低いものである。 However, according to the example of this publication, the sputtering target for forming the transparent conductive film is not a sintered body but a green compact, and the transparent conductive film is formed by a high-frequency magnetron sputtering apparatus. That is, the sputtering target has a high resistance and a DC magnetron cannot be used. The formed transparent conductive film has a resistivity as high as 1.7 × 10 −3 to 3.4 × 10 −3 Ω · cm, but has a very low light transmittance of 82 to 83%. Is.
一方、本出願人は、先に、ＤＣマグネトロンスパッタリング装置で使用できる程度のバルク抵抗を有するが、形成される透明導電膜が高抵抗で且つ光透過率が高いスパッタリングターゲットとして、酸化珪素などの絶縁性酸化物を添加した高抵抗透明導電膜用スパッタリングターゲットを開発した（特許文献２参照）。 On the other hand, the applicant previously has a bulk resistance that can be used in a DC magnetron sputtering apparatus, but the formed transparent conductive film has a high resistance and a high light transmittance. Developed a sputtering target for a high-resistance transparent conductive film to which a conductive oxide was added (see Patent Document 2).
かかるスパッタリングターゲットによると、ＤＣマグネトロンスパッタリング装置で高抵抗透明導電膜を形成することができ、光透過率も最高で９４％と高いものが得られる。 According to such a sputtering target, a high resistance transparent conductive film can be formed with a DC magnetron sputtering apparatus, and a light transmittance as high as 94% can be obtained at the maximum.
しかしながら、その後の研究により、形成される高抵抗透明導電膜の光透過率にばらつきがあり、安定して高光透過率の膜を得るのが困難であることがわかった。よって、近年における技術革新に基づいて開発される小型且つ省エネルギー化を図った装置に対応するためには、高抵抗で且つ高光透過率の高抵抗透明導電膜が確実に且つ安定して得られる技術が待望されている。 However, subsequent studies have revealed that the light transmittance of the formed high-resistance transparent conductive film varies, and it is difficult to stably obtain a film having a high light transmittance. Therefore, in order to cope with a small and energy-saving device developed on the basis of recent technological innovation, a high resistance transparent conductive film having high resistance and high light transmittance can be obtained reliably and stably. Is awaited.
なお、酸化珪素を含有するスパッタリングターゲットは古くから知られているが（特許文献３、４参照）、これら公報に開示された発明はスパッタリングターゲットを使用して形成した膜の膜欠陥の解消や導電率の向上を目指したものであり、酸化珪素の含有量は０．１重量％程度と微量である。 Note that sputtering targets containing silicon oxide have been known for a long time (see Patent Documents 3 and 4). However, the inventions disclosed in these publications eliminate film defects in a film formed by using a sputtering target and conduct electricity. The content of silicon oxide is as small as about 0.1% by weight.
また、酸化珪素を含有させることにより、低抵抗で且つ非結晶の膜を得る技術が提案されている（特許文献５、６参照）。さらに、酸化珪素を含有するが高抵抗物質の酸化シリコン相が存在しないスパッタリングターゲットにより低抵抗を成膜する技術も提案されている（特許文献７参照）。 In addition, a technique for obtaining an amorphous film with low resistance by containing silicon oxide has been proposed (see Patent Documents 5 and 6). Furthermore, a technique for forming a low resistance film by using a sputtering target that contains silicon oxide but does not have a silicon oxide phase of a high resistance substance has been proposed (see Patent Document 7).
しかしながら、特許文献５に開示されたシリコン含有膜は、比抵抗が８．８×１０−４Ω・ｃｍ以下であり、光透過率が８５〜９０％のものである。また、特許文献６には酸化珪素の添加率が大きくなると膜の抵抗率が上昇し、酸化珪素含有量が５重量％で比抵抗が１．７×１０−３Ω・ｃｍ程度、含有量が１０重量％で比抵抗が２１×１０−３Ω・ｃｍ程度と高抵抗の膜が開示されているが、光透過率についての検討はされていない。また、特許文献７に開示された膜の比抵抗は５．６×１０−４Ω・ｃｍ以下であり、光透過率の検討はされていない。 However, the silicon-containing film disclosed in Patent Document 5 has a specific resistance of 8.8 × 10 −4 Ω · cm or less and a light transmittance of 85 to 90%. Further, in Patent Document 6, the resistivity of the film increases as the addition rate of silicon oxide increases, the silicon oxide content is 5% by weight, the specific resistance is about 1.7 × 10 −3 Ω · cm, and the content is Although a film having a high resistance of 10% by weight and a specific resistance of about 21 × 10 −3 Ω · cm is disclosed, the light transmittance has not been studied. The specific resistance of the film disclosed in Patent Document 7 is 5.6 × 10 −4 Ω · cm or less, and the light transmittance has not been studied.
本発明は、このような事情に鑑み、基本的にはＤＣマグネトロンスパッタリング装置で使用でき、高抵抗で光透過率が非常に高い膜を確実に且つ安定して成膜できる高抵抗透明導電膜用スパッタリングターゲット及びそれを用いた高抵抗透明導電膜並びにその製造方法を提供することを課題とする。 In view of such circumstances, the present invention is basically used for a high resistance transparent conductive film that can be used in a DC magnetron sputtering apparatus and can reliably and stably form a film having high resistance and very high light transmittance. It is an object of the present invention to provide a sputtering target, a high resistance transparent conductive film using the sputtering target, and a manufacturing method thereof.
前記課題を解決する本発明の第１の態様は、抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗透明導電膜を形成するための高抵抗透明導電膜用スパッタリングターゲットであって、酸化インジウムと必要に応じて酸化錫を含有すると共に酸化珪素を含有し、相対密度が１００％以上であり、且つＦｅ濃度が１５ｐｐｍ以下であり、Ａｌ及びＺｒがそれぞれ１０ｐｐｍ以上含有されていることを特徴とする高抵抗透明導電膜用スパッタリングターゲットにある。
The first aspect of the present invention that solves the above-mentioned problems is for a high-resistance transparent conductive film for forming a high-resistance transparent conductive film having a resistivity of 0.9 × 10 −3 to 10 × 10 −3 Ω · cm. a sputtering target, if necessary and indium oxide containing silicon oxide while containing tin oxide, and a relative density of 100% or more, and Fe concentration Ri der less 15 ppm, Al and Zr, respectively 10ppm It exists in the sputtering target for high resistance transparent conductive films characterized by being contained above .
かかる第１の態様では、不純物として混入する可能性のあるＡｌ及びＺｒがそれぞれ１０ｐｐｍ以上含有されていても、Ｆｅ濃度を１５ｐｐｍ以下とすることにより、抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗で光透過率が高い透明導電膜が安定し且つ確実に得られる高抵抗透明導電膜用スパッタリングターゲットを提供できる。
In such a first aspect, even if Al and Zr , which may be mixed as impurities, are each contained in an amount of 10 ppm or more , the resistivity is 0.9 × 10 −3 to 10 by setting the Fe concentration to 15 ppm or less. It is possible to provide a sputtering target for a high resistance transparent conductive film in which a transparent conductive film having a high resistance of × 10 −3 Ω · cm and a high light transmittance can be obtained stably and reliably.
本発明の第２の態様は、第１記載の高抵抗透明導電膜用スパッタリングターゲットにおいて、前記酸化珪素が４〜７質量％含有されていることを特徴とする高抵抗透明導電膜用スパッタリングターゲットにある。
A second aspect of the present invention, in the high-resistance transparent conductive film, a sputtering target for the first SL placement, high-resistance transparent conductive film for a sputtering target, wherein the silicon oxide is contained 4-7 wt% It is in.
かかる第２の態様では、酸化珪素が４〜７質量％含有されているので、抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗で光透過率が高い透明導電膜がさらに安定し且つ確実に得られる。
In the second aspect, since 4 to 7% by mass of silicon oxide is contained, the resist has a high resistance of 0.9 × 10 −3 to 10 × 10 −3 Ω · cm and has a high light transmittance. A conductive film can be obtained more stably and reliably.
本発明の第３の態様は、第１又は２の態様に記載の高抵抗透明導電膜用スパッタリングターゲットにおいて、錫（Ｓｎ）がインジウム１モルに対して０〜０．３モル含有されていることを特徴とする高抵抗透明導電膜用スパッタリングターゲットにある。
According to a third aspect of the present invention, in the sputtering target for a high resistance transparent conductive film according to the first or second aspect, 0 to 0.3 mol of tin (Sn) is contained with respect to 1 mol of indium. A sputtering target for a high-resistance transparent conductive film characterized by
かかる第３の態様では、酸化インジウムを主体とし、酸化錫を所定量含有する酸化インジウム系透明導電膜となる。
In the third aspect, the indium oxide-based transparent conductive film is mainly composed of indium oxide and contains a predetermined amount of tin oxide.
本発明の第４の態様は、酸化インジウムと必要に応じて酸化錫を含有すると共に酸化珪素を含有し、抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍであり、Ｆｅ濃度が１５ｐｐｍ以下であり、Ａｌ及びＺｒがそれぞれ１０ｐｐｍ以上含有されていることを特徴とする高抵抗透明導電膜にある。
The fourth aspect of the present invention contains indium oxide and, if necessary, tin oxide and silicon oxide, and has a resistivity of 0.9 × 10 −3 to 10 × 10 −3 Ω · cm, Fe concentration Ri der less 15 ppm, in the high-resistance transparent conductive film that is characterized in that Al and Zr are contained respectively 10ppm or more.
かかる第４の態様では、不純物として混入する可能性のあるＡｌ及びＺｒがそれぞれ１０ｐｐｍ以上含有されていても、Ｆｅ濃度を１５ｐｐｍ以下とすることにより、確実に且つ安定し抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗で光透過率が高い透明導電膜となる。
In the fourth aspect, even if Al and Zr , which may be mixed as impurities, are each contained in an amount of 10 ppm or more, by making the Fe concentration 15 ppm or less, the resistivity is reliably and stably 0.9 ×. It becomes a transparent conductive film having a high resistance of 10 −3 to 10 × 10 −3 Ω · cm and a high light transmittance.
本発明の第５の態様は、第４の態様に記載の高抵抗透明導電膜において、前記酸化珪素が４〜７質量％含有されていることを特徴とする高抵抗透明導電膜にある。
A fifth aspect of the present invention is the high resistance transparent conductive film according to the fourth aspect, wherein the silicon oxide is contained in an amount of 4 to 7% by mass.
かかる第５の態様では、酸化珪素が４〜７質量％含有されているので、さらに確実に且つ安定して抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗で光透過率が高い透明導電膜となる。
In the fifth aspect, since silicon oxide is contained in an amount of 4 to 7% by mass, the resistivity is more reliably and stably high resistance of 0.9 × 10 −3 to 10 × 10 −3 Ω · cm. Thus, a transparent conductive film with high light transmittance is obtained.
本発明の第６の態様は、第４又は５の態様に記載の高抵抗透明導電膜において、錫（Ｓｎ）がインジウム１モルに対して０〜０．３モル含有されていることを特徴とする高抵抗透明導電膜にある。
According to a sixth aspect of the present invention, in the high resistance transparent conductive film according to the fourth or fifth aspect, 0 to 0.3 mol of tin (Sn) is contained with respect to 1 mol of indium. A high resistance transparent conductive film.
かかる第６の態様では、酸化インジウムを主体とし、酸化錫を所定量含有する酸化インジウム系透明導電膜となる。
In the sixth aspect, the indium oxide-based transparent conductive film is mainly composed of indium oxide and contains a predetermined amount of tin oxide.
本発明の第７の態様は、第４〜６の何れかの態様に記載の高抵抗透明導電膜において、最適酸素分圧で成膜した、１２００Åの膜の波長５５０ｎｍの光透過率が９５％以上と同等の光透過率を有する膜であることを特徴とする高抵抗透明導電膜にある。
According to a seventh aspect of the present invention, in the high resistance transparent conductive film according to any one of the fourth to sixth aspects, a light transmittance at a wavelength of 550 nm of a film having a thickness of 1200 mm formed at an optimum oxygen partial pressure is 95%. The high resistance transparent conductive film is a film having a light transmittance equivalent to that described above .
かかる第７の態様では、最適酸素分圧で成膜した、１２００Åの膜の波長５５０ｎｍの光透過率が９５％以上と同等の光透過率を有する透明導電膜となり、省エネルギー化を図った装置に適用することができる。
In the seventh aspect, a transparent conductive film having a light transmittance equivalent to 95% or more of the light transmittance at a wavelength of 550 nm of a 1200-mm film formed at an optimum oxygen partial pressure is obtained, and the apparatus is designed to save energy. Can be applied.
本発明の第８の態様は、酸化インジウムと必要に応じて酸化錫を含有すると共に酸化珪素を含有し、相対密度が１００％以上であり、且つＦｅ濃度が１５ｐｐｍ以下であり、Ａｌ及びＺｒがそれぞれ１０ｐｐｍ以上含有されている酸化インジウム系スパッタリングターゲットを用い、０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗透明導電膜を形成することを特徴とする高抵抗透明導電膜の製造方法にある。
An eighth aspect of the present invention may optionally indium oxide containing silicon oxide while containing tin oxide, and a relative density of 100% or more, and Fe concentration Ri der less 15 ppm, Al and Zr High-resistance transparent conductive film, characterized in that a high-resistance transparent conductive film of 0.9 × 10 −3 to 10 × 10 −3 Ω · cm is formed using an indium oxide-based sputtering target each containing 10 ppm or more It is in the manufacturing method of a film | membrane.
かかる第８の態様では、不純物として混入する可能性のあるＡｌ及びＺｒがそれぞれ１０ｐｐｍ以上含有されていても、Ｆｅ濃度を１５ｐｐｍ以下とすることにより、確実に且つ安定し抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗で光透過率が高い透明導電膜を得ることができる。
In the eighth aspect, even if Al and Zr , which may be mixed as impurities, are each contained in an amount of 10 ppm or more, by making the Fe concentration 15 ppm or less, the resistivity is reliably and stably 0.9 ×. A transparent conductive film having a high resistance of 10 −3 to 10 × 10 −3 Ω · cm and a high light transmittance can be obtained.
本発明の第９の態様は、第８の態様に記載の高抵抗透明導電膜の製造方法において、前記スパッタリングターゲットに前記酸化珪素が４〜７質量％含有されていることを特徴とする高抵抗透明導電膜の製造方法にある。
According to a ninth aspect of the present invention, in the method for producing a high-resistance transparent conductive film according to the eighth aspect, the sputtering target contains 4 to 7% by mass of the silicon oxide. It exists in the manufacturing method of a transparent conductive film.
かかる第９の態様では、酸化珪素が４〜７質量％含有されているので、さらに確実に且つ安定して抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗で光透過率が高い透明導電膜を得ることができる。
In the ninth aspect, since silicon oxide is contained in an amount of 4 to 7% by mass, the resistivity is 0.9 × 10 −3 to 10 × 10 −3 Ω · cm more reliably and stably. A transparent conductive film having a high light transmittance can be obtained.
本発明の第１０の態様は、第８又は９の態様に記載の高抵抗透明導電膜の製造方法において、前記スパッタリングターゲットに錫（Ｓｎ）がインジウム１モルに対して０〜０．３モル含有されていることを特徴とする高抵抗透明導電膜の製造方法にある。
According to a tenth aspect of the present invention, in the method for producing a high-resistance transparent conductive film according to the eighth or ninth aspect, the sputtering target contains 0 to 0.3 mol of tin (Sn) with respect to 1 mol of indium. It exists in the manufacturing method of the high resistance transparent conductive film characterized by the above-mentioned.
かかる第１０の態様では、酸化インジウムを主体とし、酸化錫を所定量含有する酸化インジウム系透明導電膜を得ることができる。
In the tenth aspect, an indium oxide-based transparent conductive film containing mainly indium oxide and containing a predetermined amount of tin oxide can be obtained.
本発明の第１１の態様は、第８〜１０の何れかの態様に記載の高抵抗透明導電膜の製造方法において、最適酸素分圧で成膜した、１２００Åの膜の波長５５０ｎｍの光透過率が９５％以上と同等の光透過率を有する膜を製造することを特徴とする高抵抗透明導電膜の製造方法にある。
According to an eleventh aspect of the present invention, in the method for producing a high resistance transparent conductive film according to any one of the eighth to tenth aspects, a light transmittance at a wavelength of 550 nm of a 1200 mm film formed at an optimum oxygen partial pressure is provided. Is a method for producing a high-resistance transparent conductive film, wherein a film having a light transmittance equivalent to 95% or more is produced.
かかる第１１の態様では、最適酸素分圧で成膜した、１２００Åの膜の波長５５０ｎｍの光透過率が９５％以上と同等の光透過率を有する透明導電膜を得ることができ、省エネルギー化を図った装置に適用することができる。
In the eleventh aspect, it is possible to obtain a transparent conductive film having a light transmittance equivalent to 95% or more of a light transmittance at a wavelength of 550 nm of a 1200 膜 film formed at an optimum oxygen partial pressure, thereby saving energy. It can be applied to the apparatus shown.
以上説明したように、本発明によれば、基本的にはＤＣマグネトロンスパッタリング装置で使用でき、高抵抗で光透過率が非常に高い膜を確実に且つ安定して成膜できる高抵抗透明導電膜用スパッタリングターゲット及びそれを用いた高抵抗透明導電膜及びその製造方法を提供することができる。 As described above, according to the present invention, a high-resistance transparent conductive film that can be used in a DC magnetron sputtering apparatus and can reliably and stably form a film with high resistance and very high light transmittance. Sputtering target, high resistance transparent conductive film using the same, and method for producing the same can be provided.
本発明の高抵抗透明導電膜用スパッタリングターゲットは抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗透明導電膜を形成するための高抵抗透明導電膜用酸化インジウム系スパッタリングターゲットであり、酸化インジウムを主体とし、必要に応じて酸化錫を含有すると共に酸化珪素を含有し、相対密度が１００％以上であり、且つＦｅ濃度が１５ｐｐｍ以下、好ましくは１０ｐｐｍ以下である酸化物焼結体であり、各々の酸化物は、その酸化物のまま、あるいは複合酸化物として、あるいは固溶体として存在していればよく、特に限定されない。 The sputtering target for a high resistance transparent conductive film of the present invention is an indium oxide for a high resistance transparent conductive film for forming a high resistance transparent conductive film having a resistivity of 0.9 × 10 −3 to 10 × 10 −3 Ω · cm. A sputtering target comprising mainly indium oxide, containing tin oxide as necessary and silicon oxide, having a relative density of 100% or more and an Fe concentration of 15 ppm or less, preferably 10 ppm or less. It is an oxide sintered body, and each oxide is not particularly limited as long as the oxide remains as it is, a composite oxide, or a solid solution.
本発明は、酸化インジウムを主体とし、必要に応じて酸化錫を含有すると共に酸化珪素を含有するスパッタリングターゲットにおいては、酸化珪素とＦｅとの相互作用によるためか、Ｆｅの含有率が得られる透明導電膜の光透過性に大きく影響するという知見に基づいて完成されたものである。すなわち、このようなスパッタリングターゲットを製造する際には、原料となる酸化珪素と共にＦｅ（酸化鉄）が混入する虞が増大し、このように混入するＦｅの量により光透過性が大きく変動することを知見し、本発明を完成させたものである。なお、このように酸化珪素と共に混入して光透過率に影響を与えるのはＦｅであり、他の不純物であるＡｌ及びＺｒなどは光透過性に影響を与えることがないことも判明した。よって、ＡｌやＺｒはそれぞれ１０ｐｐｍ以上含有されていてもよい。 The present invention is mainly made of indium oxide, and if necessary, a sputtering target containing tin oxide and also containing silicon oxide is transparent because of the interaction between silicon oxide and Fe. It was completed based on the knowledge that it greatly affects the light transmittance of the conductive film. That is, when manufacturing such a sputtering target, there is an increased possibility that Fe (iron oxide) is mixed with silicon oxide as a raw material, and the light transmittance greatly varies depending on the amount of Fe mixed in this way. And the present invention has been completed. It has also been found that it is Fe that mixes with silicon oxide and affects the light transmittance, and other impurities such as Al and Zr do not affect the light transmittance. Therefore, Al or Zr may be contained in an amount of 10 ppm or more.
この点をさらに詳言すると、本発明者らは、ＩＴＯ−ＳｉＯ２膜の光透過率のばらつきの原因を探るために、原料、特にＳｉＯ２の原料粉の検討、原料の解砕方法等を検討した。一般に、粉を解砕するには、ボールミルを使用するがそのボールには、アルミナ製やジルコニア製のものが存在する。これらを検討した結果、特にボールミルのボールに起因するＡｌやＺｒの不純物よりも、Ｆｅの不純物量が透過率については顕著に影響を及ぼすことが分かった。すなわち、Ｆｅ不純物濃度を抑えることによって、透過率が向上し、ばらつきも抑えられることが分かった。ここで、不純物とは通常の工程において混入する不純物であり、原料中に混入する不純物、製造過程で混入する不純物をいう。 In further detail, in order to investigate the cause of the variation in the light transmittance of the ITO-SiO 2 film, the present inventors examined the raw material, particularly the raw material powder of SiO 2 , the raw material crushing method, etc. investigated. In general, a ball mill is used to crush the powder, and the balls are made of alumina or zirconia. As a result of examining these, it was found that the amount of impurities of Fe significantly affects the transmittance more than the impurities of Al and Zr caused by the ball of the ball mill. That is, it was found that by suppressing the Fe impurity concentration, the transmittance was improved and the variation was also suppressed. Here, an impurity is an impurity mixed in a normal process, and means an impurity mixed in a raw material or an impurity mixed in a manufacturing process.
本発明のスパッタリングターゲットにおいて、酸化珪素はスパッタリングターゲットである焼結体のバルク抵抗は高くしないが、製造する透明導電膜の抵抗を高めるために用いられるもので、この目的で使用できる範囲であれば、特に限定されないが、多量に含有されると、得られる透明導電膜の光透過性が低下する傾向がある。したがって、高抵抗で且つ高光透過性の透明導電膜を得るためには、酸化珪素を４〜７質量％、好ましくは４〜６質量％含有させて焼結体とするのが好ましい。これより少ないと高抵抗の透明導電膜が得られず、一方、これより多くなると光透過率が低下するからである。 In the sputtering target of the present invention, silicon oxide does not increase the bulk resistance of the sintered body, which is the sputtering target, but is used to increase the resistance of the transparent conductive film to be produced, so long as it can be used for this purpose. Although not particularly limited, if it is contained in a large amount, the light transmittance of the transparent conductive film obtained tends to be lowered. Therefore, in order to obtain a transparent conductive film having high resistance and high light transmittance, it is preferable to contain 4 to 7% by mass, preferably 4 to 6% by mass of silicon oxide to obtain a sintered body. If the amount is less than this, a high resistance transparent conductive film cannot be obtained.
なお、ここで、スパッタリングターゲットから透明導電膜を製造するとは、最適酸素分圧下での成膜をいい、最適酸素分圧とは、酸素分圧を変化させた場合の抵抗率が最も下がる点の酸素分圧をいう。このように最適酸素分圧での成膜と規定するのは、一般的に、ＩＴＯ系の膜においては、スパッタ中に導入する酸素ガスの分圧によって抵抗率、透過率が変化し、最適酸素分圧より酸素が少なくなると膜が茶色くなる傾向になり透過率が悪化し、抵抗率も上昇するが、最適酸素分圧より酸素が多くなると透過率はほぼ維持されるが、抵抗率が大きくなる、というように、条件によって透過率や抵抗率が変化してしまうからである。 Here, producing a transparent conductive film from a sputtering target refers to film formation under an optimum oxygen partial pressure, and the optimum oxygen partial pressure is the point at which the resistivity when the oxygen partial pressure is changed is the lowest. Oxygen partial pressure. In general, in the case of an ITO-based film, the resistivity and the transmittance change depending on the partial pressure of oxygen gas introduced during sputtering, and the optimum oxygen partial pressure is defined as the film formation with the optimum oxygen partial pressure. When the oxygen is lower than the partial pressure, the membrane tends to be brown and the permeability is deteriorated and the resistivity is increased, but when the oxygen is increased more than the optimum oxygen partial pressure, the permeability is almost maintained, but the resistivity is increased. This is because the transmittance and resistivity change depending on the conditions.
また、本発明のスパッタリングターゲットは、相対密度を１００％以上とする必要がある。相対密度が小さいと、得られる透明導電膜の光透過率が低下する傾向にあるからである。なお、ここで、相対密度とは、理論密度に対して相対的に算出した密度であり、焼結により間化合物等が生成することにより理論組成と異なる組成となり、１００％を越えることもある。 Moreover, the sputtering target of this invention needs to make a relative density 100% or more. This is because if the relative density is small, the light transmittance of the obtained transparent conductive film tends to decrease. Here, the relative density is a density calculated relative to the theoretical density, and a composition different from the theoretical composition is generated by the formation of an intercalation compound or the like by sintering, and may exceed 100%.
ここで、理論密度の算出の一例を示す。各原料であるＩｎ２Ｏ３の密度を７．１７９ｇ／ｃｍ３、ＳｎＯ２の密度を６．９５０ｇ／ｃｍ３、ＳｉＯ２の密度を２．２００ｇ／ｃｍ３とし、加重平均より算出した密度が理論密度であり、これを１００％とする。例えば、８５ｗｔ％Ｉｎ２Ｏ３−１０ｗｔ％ＳｎＯ２−５ｗｔ％ＳｉＯ２の場合の理論密度は６．４３ｇ／ｃｍ３であり、その組成で相対密度１００％の場合の実際の密度は６．４３ｇ／ｃｍ３となる。 Here, an example of calculation of theoretical density is shown. The density of each raw material, In 2 O 3 , is 7.179 g / cm 3 , the density of SnO 2 is 6.950 g / cm 3 , the density of SiO 2 is 2.200 g / cm 3, and the density calculated from the weighted average is The theoretical density, which is 100%. For example, the theoretical density in the case of 85 wt% In 2 O 3 -10 wt% SnO 2 -5 wt% SiO 2 is 6.43 g / cm 3 , and the actual density in the case of the composition having a relative density of 100% is 6.43 g. / Cm 3 .
本発明のスパッタリングターゲットにおいては、必要に応じて、錫（Ｓｎ）が含有されている。錫が含有される場合には、インジウム１モルに対して０．００１〜０．３モル、好ましくは、０．０１〜０．１５モル、より好ましくは０．０５〜０．１モルの範囲で含有されるのが望ましい。この範囲内であれば、スパッタリングターゲットのキャリア電子の密度並びに移動度を適切にコントロールして導電性を良好な範囲に保つことができる。また、この範囲を越えて添加すると、スパッタリングターゲットのキャリア電子の移動度を低下させると共に導電性を劣化させる方向に働くので好ましくない。 The sputtering target of the present invention contains tin (Sn) as necessary. When tin is contained, 0.001 to 0.3 mol, preferably 0.01 to 0.15 mol, more preferably 0.05 to 0.1 mol, relative to 1 mol of indium. It is desirable to contain. Within this range, the density and mobility of carrier electrons of the sputtering target can be appropriately controlled to keep the conductivity within a good range. Further, addition beyond this range is not preferable because the mobility of carrier electrons in the sputtering target is lowered and the conductivity is deteriorated.
かかる本発明の高抵抗透明導電膜用スパッタリングターゲットは、ＤＣマグネトロンスパッタリングでスパッタリング可能な程度の抵抗値、例えば、１０−４Ω・ｃｍ台の抵抗率を有しているが、抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗透明導電膜を形成することができる。 The sputtering target for a high resistance transparent conductive film of the present invention has a resistance value that can be sputtered by DC magnetron sputtering, for example, a resistivity on the order of 10 −4 Ω · cm. A high-resistance transparent conductive film of 9 × 10 −3 to 10 × 10 −3 Ω · cm can be formed.
なお、勿論、高周波マグネトロンスパッタリング装置を用いて抵抗率が０．９×１０−３〜１０×１０−３Ω・ｃｍの高抵抗透明導電膜を形成してもよい。 Of course, a high-resistance transparent conductive film having a resistivity of 0.9 × 10 −3 to 10 × 10 −3 Ω · cm may be formed using a high-frequency magnetron sputtering apparatus.
また、本発明のスパッタリングターゲットによると、最適酸素分圧で成膜した１２００Åの膜の波長５５０ｎｍの光透過率が９５％以上であるという高光透過率の透明導電膜を確実に且つ安定して得ることができ、省エネルギー化を図った装置に適用することができる。 Further, according to the sputtering target of the present invention, a transparent conductive film having a high light transmittance in which the light transmittance at a wavelength of 550 nm of a 1200-nm film formed at an optimum oxygen partial pressure is 95% or more can be obtained reliably and stably. Therefore, the present invention can be applied to an apparatus that saves energy.
次に、本発明のスパッタリングターゲットの製造方法について説明するが、これは単に例示したものであり、製造方法は特に限定されるものではない。 Next, although the manufacturing method of the sputtering target of this invention is demonstrated, this is only illustrated and the manufacturing method is not specifically limited.
まず、本発明のスパッタリングターゲットを構成する出発原料としては、一般的にＩｎ２Ｏ３、ＳｎＯ２、ＳｉＯ２の粉末である。さらに、これらの単体、化合物、複合酸化物等を原料としてもよい。単体、化合物を使う場合はあらかじめ酸化物にするようなプロセスを通すようにする。なお、ここで、重要なのは、不純物であるＦｅ濃度がスパッタリングターゲットにおいて１５ｐｐｍ以下となるような原料を用いることである。 First, the starting material constituting the sputtering target of the present invention is generally In 2 O 3 , SnO 2 , SiO 2 powder. Furthermore, these simple substances, compounds, complex oxides, and the like may be used as raw materials. When using a simple substance or a compound, it is made to go through a process of making it oxide in advance. Here, it is important to use a raw material whose Fe concentration as an impurity is 15 ppm or less in the sputtering target.
これらの原料粉を、所望の配合率で混合し、成形する方法は特に限定されず、従来から公知の各種湿式法又は乾式法を用いることができる。 A method of mixing and molding these raw material powders at a desired mixing ratio is not particularly limited, and various conventionally known wet methods or dry methods can be used.
乾式法としては、コールドプレス（Ｃｏｌｄ Ｐｒｅｓｓ）法やホットプレス（Ｈｏｔ Ｐｒｅｓｓ）法等を挙げることができる。コールドプレス法では、混合粉を成形型に充填して成形体を作製し、大気雰囲気下または酸素雰囲気下で焼成・焼結させる。ホットプレス法では、混合粉を成形型内で直接焼結させる。 Examples of the dry method include a cold press method and a hot press method. In the cold press method, a mixed powder is filled in a mold to produce a molded body, which is fired and sintered in an air atmosphere or an oxygen atmosphere. In the hot press method, the mixed powder is directly sintered in a mold.
湿式法としては、例えば、濾過式成形法（特開平１１−２８６００２号公報参照）を用いるのが好ましい。この濾過式成形法は、セラミックス原料スラリーから水分を減圧排水して成形体を得るための非水溶性材料からなる濾過式成形型であって、１個以上の水抜き孔を有する成形用下型と、この成形用下型の上に載置した通水性を有するフィルターと、このフィルターをシールするためのシール材を介して上面側から挟持する成形用型枠からなり、前記成形用下型、成形用型枠、シール材、およびフィルターが各々分解できるように組立てられており、該フィルター面側からのみスラリー中の水分を減圧排水する濾過式成形型を用い、混合粉、イオン交換水と有機添加剤からなるスラリーを調製し、このスラリーを濾過式成形型に注入し、該フィルター面側からのみスラリー中の水分を減圧排水して成形体を作製し、得られたセラミックス成形体を乾燥脱脂後、焼成する。 As the wet method, for example, it is preferable to use a filtration molding method (see JP-A-11-286002). This filtration molding method is a filtration molding die made of a water-insoluble material for obtaining a molded body by draining water from a ceramic raw material slurry under reduced pressure, and a lower molding die having one or more drain holes And a water-permeable filter placed on the molding lower mold, and a molding mold clamped from the upper surface side through a sealing material for sealing the filter, the molding lower mold, Forming mold, sealing material, and filter are assembled so that they can be disassembled respectively. Using a filtration mold that drains water in the slurry under reduced pressure only from the filter surface side, mixed powder, ion-exchanged water and organic A slurry made of an additive was prepared, this slurry was poured into a filtration mold, and the molded body was produced by draining the water in the slurry under reduced pressure only from the filter surface side. After drying degreasing, and firing.
各方法において、焼成温度は１３００〜１６００℃が好ましく、さらに好ましくは、１３００〜１４５０℃である。その後、所定寸法に成形・加工のための機械加工を施しターゲットとする。 In each method, the firing temperature is preferably 1300 to 1600 ° C, more preferably 1300 to 1450 ° C. Thereafter, machining for forming / processing is performed to a predetermined dimension to obtain a target.
以下、本発明を実施例に基づいて説明するが、これに限定されるものではない。なお、以下の各実施例及び各比較例においては、ＳｉＯ２粉として種々の純度のものを用いてこれによりＦｅ不純物濃度を変化させ、また、原料粉の解砕工程において、アルミナボールを使用したボールミルの時間及びジルコニアボールを使用したボールミルの時間を変更することにより、Ａｌ不純物濃度及びＺｒ不純物濃度を変化させた。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, it is not limited to this. In each of the following Examples and Comparative Examples, SiO 2 powders having various purities were used, thereby changing the Fe impurity concentration, and alumina balls were used in the raw material powder crushing step. The Al impurity concentration and the Zr impurity concentration were changed by changing the time of the ball mill and the time of the ball mill using zirconia balls.
（実施例１）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度＞９９．０％のＳｉＯ２粉を用意した。この粉末を、ＳｎＯ２ １０ｗｔ％、ＳｉＯ２ ４ｗｔ％、Ｉｎ２Ｏ３ ８６ｗｔ％の比率で全量で約１．５Ｋｇ用意し、これを樹脂製ポットに投入し、ジルコニアボール・アルミナボールでそれぞれ所定の時間、乾式ボールミル、湿式ボールミルを行い、得られたスラリーを濾過式形成法によって成形体を得た。この成形体を大気雰囲気にて、室温から１４００℃まで４００℃／ｈで昇温し、１４５０℃にて８ｈ保持し、３００℃／ｈで常温まで降温した。この焼結体を直径６ｉｎｃｈ×厚さ６ｍｍに加工し、無酸素銅製のバッキングプレートにメタルボンディングしてスパッタリングターゲットを得た。加工の際、スパッタリング面は＃１７０砥石により平面研削を行った。このターゲットのバルク抵抗率は２．０×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は１０ｐｐｍ、Ａｌ濃度は２５ｐｐｍ、Ｚｒ濃度は６５ｐｐｍであった。
Example 1
In 2 O 3 powder and SnO 2 powder with a purity> 99.99%, and SiO 2 powder with a purity> 99.0% were prepared. About 1.5 Kg of this powder was prepared in a total amount of SnO 2 10 wt%, SiO 2 4 wt%, In 2 O 3 86 wt%, and this was put into a resin pot, and each of these powders was stipulated with zirconia balls and alumina balls. Time, a dry ball mill, and a wet ball mill were performed, and a molded body was obtained from the resulting slurry by a filtration method. The molded body was heated from room temperature to 1400 ° C. at 400 ° C./h, held at 1450 ° C. for 8 h, and cooled to room temperature at 300 ° C./h in the air atmosphere. This sintered body was processed to a diameter of 6 inches × thickness of 6 mm, and metal bonded to an oxygen-free copper backing plate to obtain a sputtering target. At the time of processing, the sputtering surface was subjected to surface grinding with a # 170 grindstone. The bulk resistivity of this target was 2.0 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 10 ppm, the Al concentration was 25 ppm, and the Zr concentration was 65 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（実施例２）
純度＞９９．９％のＳｉＯ２粉を用いた以外は実施例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．０×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５ｐｐｍ未満、Ａｌ濃度は２５ｐｐｍ、Ｚｒ濃度は３０ｐｐｍであった。
(Example 2)
A sintered body was obtained in the same manner as in Example 1 except that SiO 2 powder having a purity of> 99.9% was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.0 × 10 −4 Ω · cm. Further, the Fe concentration in this target was less than 5 ppm, the Al concentration was 25 ppm, and the Zr concentration was 30 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（実施例３）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度＞９９．０％のＳｉＯ２粉を、ＳｎＯ２ １０ｗｔ％、ＳｉＯ２ ５ｗｔ％、Ｉｎ２Ｏ３ ８５ｗｔ％の比率で用いた以外は実施例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．２×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は１０ｐｐｍ、Ａｌ濃度は１５ｐｐｍ、Ｚｒ濃度は６０ｐｐｍであった。
(Example 3)
In 2 O 3 powder and SnO 2 powder with a purity> 99.99%, and SiO 2 powder with a purity> 99.0% at a ratio of SnO 2 10 wt%, SiO 2 5 wt%, In 2 O 3 85 wt% A sintered body was obtained in the same manner as in Example 1 except that. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.2 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 10 ppm, the Al concentration was 15 ppm, and the Zr concentration was 60 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（実施例４）
純度＞９９．９％のＳｉＯ２粉を用いた以外は実施例３と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．２×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５ｐｐｍ未満、Ａｌ濃度は３０ｐｐｍ、Ｚｒ濃度は５０ｐｐｍであった。
Example 4
A sintered body was obtained in the same manner as in Example 3 except that SiO 2 powder having a purity of> 99.9% was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.2 × 10 −4 Ω · cm. Further, the Fe concentration in this target was less than 5 ppm, the Al concentration was 30 ppm, and the Zr concentration was 50 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（実施例５）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度＞９９．９％のＳｉＯ２粉を、ＳｎＯ２ ５ｗｔ％、ＳｉＯ２ ５ｗｔ％、Ｉｎ２Ｏ３ ９０ｗｔ％の比率で用いた以外は実施例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．３×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５ｐｐｍ以下、Ａｌ濃度は２５ｐｐｍ、Ｚｒ濃度は７５ｐｐｍであった。
(Example 5)
In 2 O 3 powder and SnO 2 powder with a purity of> 99.99%, and SiO 2 powder with a purity of> 99.9% are used in a ratio of SnO 2 5 wt%, SiO 2 5 wt%, In 2 O 3 90 wt%. A sintered body was obtained in the same manner as in Example 1 except that. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.3 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 5 ppm or less, the Al concentration was 25 ppm, and the Zr concentration was 75 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（実施例６）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度＞９９．９％のＳｉＯ２粉を、ＳｎＯ２ １５ｗｔ％、ＳｉＯ２ ５ｗｔ％、Ｉｎ２Ｏ３ ８０ｗｔ％の比率で用いた以外は実施例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．７×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５ｐｐｍ未満、Ａｌ濃度は１５ｐｐｍ、Ｚｒ濃度は４０ｐｐｍであった。
(Example 6)
Purity> 99.99% In 2 O 3 powder and SnO 2 powder, and further use> 29.9% SiO 2 powder at a ratio of SnO 2 15 wt%, SiO 2 5 wt%, In 2 O 3 80 wt% A sintered body was obtained in the same manner as in Example 1 except that. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.7 × 10 −4 Ω · cm. Further, the Fe concentration in this target was less than 5 ppm, the Al concentration was 15 ppm, and the Zr concentration was 40 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（実施例７）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度＞９９．０％のＳｉＯ２粉を、ＳｎＯ２ １０ｗｔ％、ＳｉＯ２ ６ｗｔ％、Ｉｎ２Ｏ３ ８４ｗｔ％の比率で用いた以外は実施例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．５×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は１０ｐｐｍ、Ａｌ濃度は２０ｐｐｍ、Ｚｒ濃度は８０ｐｐｍであった。
(Example 7)
In 2 O 3 powder and SnO 2 powder with a purity> 99.99%, and SiO 2 powder with a purity> 99.0% are used in a ratio of SnO 2 10 wt%, SiO 2 6 wt%, In 2 O 3 84 wt%. A sintered body was obtained in the same manner as in Example 1 except that. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.5 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 10 ppm, the Al concentration was 20 ppm, and the Zr concentration was 80 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（実施例８）
純度＞９９．９％のＳｉＯ２粉を用いた以外は実施例７と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．５×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５ｐｐｍ未満、Ａｌ濃度は２０ｐｐｍ、Ｚｒ濃度は６０ｐｐｍであった。
(Example 8)
A sintered body was obtained in the same manner as in Example 7 except that SiO 2 powder having a purity of> 99.9% was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.5 × 10 −4 Ω · cm. Further, the Fe concentration in this target was less than 5 ppm, the Al concentration was 20 ppm, and the Zr concentration was 60 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（実施例９）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度＞９９．０％のＳｉＯ２粉を、ＳｎＯ２ １０ｗｔ％、ＳｉＯ２ ７ｗｔ％、Ｉｎ２Ｏ３ ８３ｗｔ％の比率で用いた以外は実施例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．８×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は１５ｐｐｍ、Ａｌ濃度は２０ｐｐｍ、Ｚｒ濃度は７０ｐｐｍであった。
Example 9
In 2 O 3 powder and SnO 2 powder with a purity of> 99.99%, and SiO 2 powder with a purity of> 99.0% are used in a ratio of SnO 2 10 wt%, SiO 2 7 wt%, In 2 O 3 83 wt%. A sintered body was obtained in the same manner as in Example 1 except that. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.8 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 15 ppm, the Al concentration was 20 ppm, and the Zr concentration was 70 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（実施例１０）
純度＞９９．９％のＳｉＯ２粉を用いた以外は実施例９と同様にして焼結体を得た。その後、この焼成体を酸素雰囲気下で１５５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．７×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５ｐｐｍ未満、Ａｌ濃度は３０ｐｐｍ、Ｚｒ濃度は５０ｐｐｍであった。
(Example 10)
A sintered body was obtained in the same manner as in Example 9 except that SiO 2 powder having a purity of> 99.9% was used. Thereafter, the fired body was fired and sintered at 1550 ° C. for 8 hours in an oxygen atmosphere. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.7 × 10 −4 Ω · cm. Further, the Fe concentration in this target was less than 5 ppm, the Al concentration was 30 ppm, and the Zr concentration was 50 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例１）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度不明のＳｉＯ２粉（デンカ製Ｙ−７４）を用意した。この粉末を、ＳｎＯ２ １０ｗｔ％、ＳｉＯ２ ４ｗｔ％、Ｉｎ２Ｏ３ ８６ｗｔ％の比率で全量で約１．５Ｋｇ用意し、濾過式成形法によって成形体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．０×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は７０ｐｐｍ、Ａｌ濃度は２０ｐｐｍ、Ｚｒ濃度は８０ｐｐｍであった。
(Comparative Example 1)
Purity> 99.99% In 2 O 3 powder and SnO 2 powder, and SiO 2 powder of unknown purity (Y-74 made by Denka) were prepared. About 1.5 kg of this powder was prepared in a total amount of SnO 2 10 wt%, SiO 2 4 wt%, In 2 O 3 86 wt%, and a molded body was obtained by a filtration molding method. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.0 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 70 ppm, the Al concentration was 20 ppm, and the Zr concentration was 80 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例２）
純度不明のＳｉＯ２粉（デンカ製Ｙ−１０５）を用いた以外は比較例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．０×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は３０ｐｐｍ、Ａｌ濃度は１５ｐｐｍ、Ｚｒ濃度は５５ｐｐｍであった。
(Comparative Example 2)
A sintered body was obtained in the same manner as in Comparative Example 1 except that SiO 2 powder of unknown purity (Y-105 manufactured by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.0 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 30 ppm, the Al concentration was 15 ppm, and the Zr concentration was 55 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例３）
純度不明のＳｉＯ２粉（デンカ製Ｌ−４４）を用いた以外は比較例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．１×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は２０ｐｐｍ、Ａｌ濃度は３０ｐｐｍ、Ｚｒ濃度は５０ｐｐｍであった。
(Comparative Example 3)
A sintered body was obtained in the same manner as in Comparative Example 1 except that SiO 2 powder of unknown purity (L-44 manufactured by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.1 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 20 ppm, the Al concentration was 30 ppm, and the Zr concentration was 50 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例４）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度不明のＳｉＯ２粉（デンカ製Ｙ−７４）を、ＳｎＯ２ １０ｗｔ％、ＳｉＯ２ ５ｗｔ％、Ｉｎ２Ｏ３ ８５ｗｔ％の比率で全量で約１．５Ｋｇ用意し、濾過式成形法によって成形体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．２×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は９０ｐｐｍ、Ａｌ濃度は１０ｐｐｍ、Ｚｒ濃度は５０ｐｐｍであった。
(Comparative Example 4)
Purity> 99.99% In 2 O 3 powder and SnO 2 powder, SiO 2 powder of unknown purity (Y-74 made by Denka), SnO 2 10 wt%, SiO 2 5 wt%, In 2 O 3 85 wt% About 1.5 kg of the total amount was prepared in a ratio, and a molded body was obtained by a filtration molding method. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.2 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 90 ppm, the Al concentration was 10 ppm, and the Zr concentration was 50 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例５）
純度不明のＳｉＯ２粉（デンカ製Ｙ−１０５）を用いた以外は比較例４と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．２×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は４０ｐｐｍ、Ａｌ濃度は３０ｐｐｍ、Ｚｒ濃度は４５ｐｐｍであった。
(Comparative Example 5)
A sintered body was obtained in the same manner as in Comparative Example 4 except that SiO 2 powder of unknown purity (Y-105 manufactured by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.2 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 40 ppm, the Al concentration was 30 ppm, and the Zr concentration was 45 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例６）
純度不明のＳｉＯ２粉（デンカ製Ｌ−４４）を用いた以外は比較例４と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．１×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は２０ｐｐｍ、Ａｌ濃度は１５ｐｐｍ、Ｚｒ濃度は７０ｐｐｍであった。
(Comparative Example 6)
A sintered body was obtained in the same manner as in Comparative Example 4 except that SiO 2 powder of unknown purity (L-44 manufactured by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.1 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 20 ppm, the Al concentration was 15 ppm, and the Zr concentration was 70 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例７）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度不明のＳｉＯ２粉（デンカ製Ｙ−７４）を、ＳｎＯ２ １０ｗｔ％、ＳｉＯ２ ６ｗｔ％、Ｉｎ２Ｏ３ ８４ｗｔ％の比率で全量で約１．５Ｋｇ用意し、濾過式成形法によって成形体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．５×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は１００ｐｐｍ、Ａｌ濃度は１５ｐｐｍ、Ｚｒ濃度は４０ｐｐｍであった。
(Comparative Example 7)
Purity> 99.99% In 2 O 3 powder and SnO 2 powder, further SiO 2 powder of unknown purity (Y-74 made by Denka), SnO 2 10 wt%, SiO 2 6 wt%, In 2 O 3 84 wt% About 1.5 kg of the total amount was prepared in a ratio, and a molded body was obtained by a filtration molding method. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.5 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 100 ppm, the Al concentration was 15 ppm, and the Zr concentration was 40 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例８）
純度不明のＳｉＯ２粉（デンカ製Ｙ−１０５）を用いた以外は比較例７と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．５×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は４０ｐｐｍ、Ａｌ濃度は１０ｐｐｍ、Ｚｒ濃度は５０ｐｐｍであった。
(Comparative Example 8)
A sintered body was obtained in the same manner as in Comparative Example 7 except that SiO 2 powder with unknown purity (Denka Y-105) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.5 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 40 ppm, the Al concentration was 10 ppm, and the Zr concentration was 50 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例９）
純度不明のＳｉＯ２粉（デンカ製Ｌ−４４）を用いた以外は比較例７と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．４×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は２５ｐｐｍ、Ａｌ濃度は２５ｐｐｍ、Ｚｒ濃度は３０ｐｐｍであった。
(Comparative Example 9)
A sintered body was obtained in the same manner as in Comparative Example 7 except that SiO 2 powder of unknown purity (L-44 manufactured by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.4 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 25 ppm, the Al concentration was 25 ppm, and the Zr concentration was 30 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例１０）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度不明のＳｉＯ２粉（デンカ製Ｙ−７４）を、ＳｎＯ２ １０ｗｔ％、ＳｉＯ２ ７ｗｔ％、Ｉｎ２Ｏ３ ８３ｗｔ％の比率で全量で約１．５Ｋｇ用意し、濾過式成形法によって成形体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．９×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は１２０ｐｐｍ、Ａｌ濃度は１０ｐｐｍ、Ｚｒ濃度は６０ｐｐｍであった。
(Comparative Example 10)
Purity> 99.99% In 2 O 3 powder and SnO 2 powder, SiO 2 powder of unknown purity (Y-74 made by Denka), SnO 2 10 wt%, SiO 2 7 wt%, In 2 O 3 83 wt% About 1.5 kg of the total amount was prepared in a ratio, and a molded body was obtained by a filtration molding method. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.9 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 120 ppm, the Al concentration was 10 ppm, and the Zr concentration was 60 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例１１）
純度不明のＳｉＯ２粉（デンカ製Ｙ−１０５）を用いた以外は比較例１０と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．８×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５０ｐｐｍ、Ａｌ濃度は２０ｐｐｍ、Ｚｒ濃度は３０ｐｐｍであった。
(Comparative Example 11)
A sintered body was obtained in the same manner as in Comparative Example 10 except that SiO 2 powder of unknown purity (Y-105 manufactured by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.8 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 50 ppm, the Al concentration was 20 ppm, and the Zr concentration was 30 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例１２）
純度不明のＳｉＯ２粉（デンカ製Ｌ−４４）を用いた以外は比較例１０と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は２．８×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は３０ｐｐｍ、Ａｌ濃度は１０ｐｐｍ、Ｚｒ濃度は４０ｐｐｍであった。
(Comparative Example 12)
A sintered body was obtained in the same manner as in Comparative Example 10 except that SiO 2 powder of unknown purity (L-44 made by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 2.8 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 30 ppm, the Al concentration was 10 ppm, and the Zr concentration was 40 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例１３）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度不明のＳｉＯ２粉（デンカ製Ｙ−７４）を、ＳｎＯ２ １０ｗｔ％、ＳｉＯ２ ３ｗｔ％、Ｉｎ２Ｏ３ ８７ｗｔ％の比率で全量で約１．５Ｋｇ用意し、濾過式成形法によって成形体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は１．８×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５０ｐｐｍ、Ａｌ濃度は１５ｐｐｍ、Ｚｒ濃度は４５ｐｐｍであった。
(Comparative Example 13)
Purity> 99.99% In 2 O 3 powder and SnO 2 powder, further SiO 2 powder of unknown purity (Y-74 made by Denka), SnO 2 10 wt%, SiO 2 3 wt%, In 2 O 3 87 wt% About 1.5 kg of the total amount was prepared in a ratio, and a molded body was obtained by a filtration molding method. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 1.8 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 50 ppm, the Al concentration was 15 ppm, and the Zr concentration was 45 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例１４）
純度不明のＳｉＯ２粉（デンカ製Ｙ−１０５）を用いた以外は比較例１３と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は１．７×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は２０ｐｐｍ、Ａｌ濃度は１０ｐｐｍ、Ｚｒ濃度は７０ｐｐｍであった。
(Comparative Example 14)
A sintered body was obtained in the same manner as Comparative Example 13 except that SiO 2 powder of unknown purity (Y-105 manufactured by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 1.7 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 20 ppm, the Al concentration was 10 ppm, and the Zr concentration was 70 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例１５）
純度不明のＳｉＯ２粉（デンカ製Ｌ−４４）を用いた以外は比較例１３と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は１．８×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は１０ｐｐｍ、Ａｌ濃度は１５ｐｐｍ、Ｚｒ濃度は３０ｐｐｍであった。
(Comparative Example 15)
A sintered body was obtained in the same manner as in Comparative Example 13 except that SiO 2 powder of unknown purity (L-44 manufactured by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 1.8 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 10 ppm, the Al concentration was 15 ppm, and the Zr concentration was 30 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例１６）
純度＞９９．０％のＳｉＯ２粉を用いた以外は比較例１３と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は１．８×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５ｐｐｍ、Ａｌ濃度は２０ｐｐｍ、Ｚｒ濃度は２５ｐｐｍであった。
(Comparative Example 16)
A sintered body was obtained in the same manner as in Comparative Example 13 except that SiO 2 powder having a purity of> 99.0% was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 1.8 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 5 ppm, the Al concentration was 20 ppm, and the Zr concentration was 25 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（比較例１７）
純度＞９９．９％のＳｉＯ２粉を用いた以外は比較例１３と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は１．８×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５ｐｐｍ未満、Ａｌ濃度は３０ｐｐｍ、Ｚｒ濃度は７０ｐｐｍであった。
(Comparative Example 17)
A sintered body was obtained in the same manner as in Comparative Example 13 except that SiO 2 powder having a purity of> 99.9% was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 1.8 × 10 −4 Ω · cm. Further, the Fe concentration in this target was less than 5 ppm, the Al concentration was 30 ppm, and the Zr concentration was 70 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（参考例１）
純度＞９９．９９％のＩｎ２Ｏ３粉およびＳｎＯ２粉、さらに純度不明のＳｉＯ２粉（デンカ製Ｙ−７４）を、ＳｎＯ２ １０ｗｔ％、ＳｉＯ２ １０ｗｔ％、Ｉｎ２Ｏ３ ８０ｗｔ％の比率で全量で約１．５Ｋｇ用意し、濾過式成形法によって成形体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は４．０×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は１７０ｐｐｍ、Ａｌ濃度は１５ｐｐｍ、Ｚｒ濃度は３０ｐｐｍであった。
(Reference Example 1)
Purity> 99.99% In 2 O 3 powder and SnO 2 powder, SiO 2 powder of unknown purity (Y-74 made by Denka), SnO 2 10 wt%, SiO 2 10 wt%, In 2 O 3 80 wt% About 1.5 kg of the total amount was prepared in a ratio, and a molded body was obtained by a filtration molding method. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 4.0 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 170 ppm, the Al concentration was 15 ppm, and the Zr concentration was 30 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（参考例２）
純度不明のＳｉＯ２粉（デンカ製Ｙ−１０５）を用いた以外は参考例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は４．１×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は７０ｐｐｍ、Ａｌ濃度は１０ｐｐｍ、Ｚｒ濃度は６０ｐｐｍであった。
(Reference Example 2)
A sintered body was obtained in the same manner as in Reference Example 1, except that SiO 2 powder of unknown purity (Y-105 manufactured by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 4.1 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 70 ppm, the Al concentration was 10 ppm, and the Zr concentration was 60 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（参考例３）
純度不明のＳｉＯ２粉（デンカ製Ｌ−４４）を用いた以外は参考例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は４．０×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は４０ｐｐｍ、Ａｌ濃度は２０ｐｐｍ、Ｚｒ濃度は４０ｐｐｍであった。
(Reference Example 3)
A sintered body was obtained in the same manner as in Reference Example 1 except that SiO 2 powder of unknown purity (L-44 manufactured by Denka) was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 4.0 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 40 ppm, the Al concentration was 20 ppm, and the Zr concentration was 40 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（参考例４）
純度＞９９．０％のＳｉＯ２粉を用いた以外は参考例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は４．０×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は１５ｐｐｍ、Ａｌ濃度は２０ｐｐｍ、Ｚｒ濃度は７０ｐｐｍであった。
(Reference Example 4)
A sintered body was obtained in the same manner as in Reference Example 1 except that SiO 2 powder having a purity of> 99.0% was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 4.0 × 10 −4 Ω · cm. Further, the Fe concentration in this target was 15 ppm, the Al concentration was 20 ppm, and the Zr concentration was 70 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（参考例５）
純度＞９９．９％のＳｉＯ２粉を用いた以外は参考例１と同様にして焼結体を得た。その後、この焼成体を大気中で１４５０℃にて８時間焼成・焼結させた。この焼結体を加工し、理論密度に対する相対密度１００％のターゲットを得た。このターゲットのバルク抵抗率は４．０×１０−４Ω・ｃｍであった。また、このターゲット中のＦｅ濃度は５ｐｐｍ未満、Ａｌ濃度は１５ｐｐｍ、Ｚｒ濃度は５０ｐｐｍであった。
(Reference Example 5)
A sintered body was obtained in the same manner as in Reference Example 1 except that SiO 2 powder having a purity of> 99.9% was used. Thereafter, the fired body was fired and sintered at 1450 ° C. for 8 hours in the air. This sintered body was processed to obtain a target having a relative density of 100% with respect to the theoretical density. The bulk resistivity of this target was 4.0 × 10 −4 Ω · cm. Further, the Fe concentration in this target was less than 5 ppm, the Al concentration was 15 ppm, and the Zr concentration was 50 ppm.
なお、ターゲット中の不純物濃度はＩＣＰ分析によって求めた。 The impurity concentration in the target was determined by ICP analysis.
（成膜実施例）
各実施例及び各比較例のスパッタリングターゲットを用いて、以下のような条件にてＤＣマグネトロンスパッタによってガラス基板上に成膜し、厚さ１２００Åの膜を得た。この膜の波長５５０ｎｍの透過率と、抵抗率を測定した。この結果を表１に示す。また、膜中のＦｅ、Ａｌ、Ｚｒ濃度も併せて示す。なお、これらの濃度は、各実施例及び各比較例の透明導電膜をガラス基板毎に複数枚溶かし、ＩＣＰ分析により測定した。
(Example of film formation)
Using the sputtering target of each Example and each Comparative Example, a film having a thickness of 1200 mm was obtained on a glass substrate by DC magnetron sputtering under the following conditions. The transmittance of the film at a wavelength of 550 nm and the resistivity were measured. The results are shown in Table 1. Also shown are the Fe, Al, and Zr concentrations in the film. In addition, these density | concentration melt | dissolved several transparent conductive films of each Example and each comparative example for every glass substrate, and measured it by ICP analysis.
ターゲット寸法 ：φ＝６ｉｎ． ｔ＝６ｍｍ
スパッタ方式 ：ＤＣマグネトロンスパッタ
排気装置 ：ロータリーポンプ＋クライオポンプ
到達真空度 ：４．０×１０−６［Ｔｏｒｒ］
Ａｒ圧力 ：３．０×１０−３［Ｔｏｒｒ］
酸素圧力 ：１〜１０×１０−５［Ｔｏｒｒ］
基板温度 ：２００℃
スパッタ電力 ：３００Ｗ （電力密度１．６Ｗ／ｃｍ２）
使用基板 ：テンパックス（液晶ディスプレイ用ガラス） ｔ＝１．８ｍｍ
Target dimension: φ = 6 in. t = 6mm
Sputtering method: DC magnetron sputtering Exhaust device: Rotary pump + cryopump Ultimate vacuum: 4.0 × 10 −6 [Torr]
Ar pressure: 3.0 × 10 −3 [Torr]
Oxygen pressure: 1-10 × 10 −5 [Torr]
Substrate temperature: 200 ° C
Sputtering power: 300 W (Power density 1.6 W / cm 2 )
Substrate used: Tempax (liquid crystal display glass) t = 1.8mm
表１の結果から、Ｆｅ濃度が１５ｐｐｍ以下、特に１０ｐｐｍ以下の実施例においては、高抵抗で且つ高光透過率という特性が両立した導電膜を得ることができ、また、ＡｌやＺｒの不純物の含有量には影響されないことがわかった。 From the results of Table 1, in Examples where the Fe concentration is 15 ppm or less, particularly 10 ppm or less, it is possible to obtain a conductive film having both high resistance and high light transmittance, and containing Al and Zr impurities. It was found that the amount was not affected.
一方、Ｆｅ濃度が１５ｐｐｍを越えるスパッタリングターゲットの比較例では、光透過率が低下し、省エネルギー装置には最適なものではないことがわかった。 On the other hand, in the comparative example of the sputtering target in which the Fe concentration exceeds 15 ppm, it was found that the light transmittance is lowered and is not optimal for the energy saving apparatus.
また、酸化珪素含有量が３％のものでは各比較例共に、抵抗率が０．８×１０−３Ω・ｃｍと小さく、目的とする高抵抗は得られないことがわかった。 It was also found that when the silicon oxide content was 3%, the resistivity was as small as 0.8 × 10 −3 Ω · cm in each of the comparative examples, and the intended high resistance could not be obtained.
なお、参考例１〜５に示すように、酸化珪素含有量が１０％と多くなると、２０×１０−３Ω・ｃｍを越える抵抗を有すると共に透過率が低下するが、Ｆｅ濃度が１５ｐｐｍ以下である参考例４，５では、従来の高抵抗薄膜と比較すると優位な光透過率を有するので、高抵抗用途での使用は可能であることがわかった。 In addition, as shown in Reference Examples 1 to 5, when the silicon oxide content increases to 10%, it has a resistance exceeding 20 × 10 −3 Ω · cm and the transmittance decreases, but the Fe concentration is 15 ppm or less. In Reference Examples 4 and 5, it has been found that the light transmittance is superior to that of the conventional high resistance thin film, so that it can be used for high resistance applications.
Claims (11)
The method for producing a high-resistance transparent conductive film according to any one of claims 8 to 10 , wherein the light transmittance at a wavelength of 550 nm of a 1200-nm film formed at an optimum oxygen partial pressure is equal to or greater than 95%. A method for producing a high-resistance transparent conductive film, comprising: producing a film having a high-resistance film.
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