JP5881681B2 - Oxide-type semiconductor material and sputtering target - Google Patents
Oxide-type semiconductor material and sputtering target Download PDFInfo
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- 239000000463 material Substances 0.000 title claims description 64
- 239000004065 semiconductor Substances 0.000 title claims description 60
- 238000005477 sputtering target Methods 0.000 title claims description 13
- 239000002019 doping agent Substances 0.000 claims description 105
- 229910052751 metal Inorganic materials 0.000 claims description 85
- 239000002184 metal Substances 0.000 claims description 82
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 229910052718 tin Inorganic materials 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims description 11
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 description 50
- 239000011135 tin Substances 0.000 description 41
- 239000011777 magnesium Substances 0.000 description 38
- 239000010408 film Substances 0.000 description 26
- 238000004544 sputter deposition Methods 0.000 description 17
- 239000011575 calcium Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 239000004973 liquid crystal related substance Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
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- 239000010409 thin film Substances 0.000 description 8
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- 230000000694 effects Effects 0.000 description 6
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- 229910052726 zirconium Inorganic materials 0.000 description 5
- 230000005355 Hall effect Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910007604 Zn—Sn—O Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、液晶ディスプレイなどの表示装置を構成する半導体素子を形成するための半導体材料に関し、特に、Ｚｎ酸化物とＳｎ酸化物を含む酸化物型半導体材料に関する。 The present invention relates to a semiconductor material for forming a semiconductor element constituting a display device such as a liquid crystal display, and more particularly to an oxide semiconductor material containing Zn oxide and Sn oxide.
近年、液晶ディスプレイに代表される薄型テレビなどの表示デバイスは、生産量の増加、大画面化の傾向が著しい。そして、その表示デバイスとしては、薄膜トランジスタ（Ｔｈｉｎ Ｆｉｌｍ Ｔｒａｎｓｉｓｔｏｒ、以下、ＴＦＴと略称する）をスイッチング素子として用いるアクティブマトリックスタイプの液晶ディスプレイが広く普及している。 In recent years, display devices such as flat-screen TVs typified by liquid crystal displays have a tendency to increase production and increase screen size. As a display device, an active matrix type liquid crystal display using a thin film transistor (hereinafter abbreviated as TFT) as a switching element is widely used.
このようなＴＦＴをスイッチング素子とした表示デバイスでは、その構成材料として酸化物型半導体材料が用いられようになっている。この酸化物型半導体材料としては、透明酸化物半導体材料の一種であるＩＧＺＯ（Ｉｎ−Ｇａ−Ｚｎ−Ｏ系酸化物）が注目されている（特許文献１参照）。このＩＧＺＯは、従来から用いられている多結晶Ｓｉ（シリコン）に次いでキャリア移動度が高く、ａ−Ｓｉ（アモルファスシリコン）のようにＴＦＴ特性の特性バラツキが小さいため、今後の半導体材料として有望なものとして広く利用されはじめている。 In a display device using such a TFT as a switching element, an oxide semiconductor material is used as a constituent material thereof. As this oxide semiconductor material, IGZO (In—Ga—Zn—O-based oxide), which is a kind of transparent oxide semiconductor material, has attracted attention (see Patent Document 1). This IGZO has the highest carrier mobility next to polycrystalline Si (silicon) that has been used in the past, and has little variation in TFT characteristics like a-Si (amorphous silicon), so it is promising as a future semiconductor material. It is beginning to be widely used as a product.
ところで、薄型テレビなどの液晶ディスプレイでは、表示方式の変化が生じている。具体的には、平面表示（２Ｄ）に加え、立体表示（３Ｄ）が可能な液晶ディスプレイが提供されている。この立体表示（３Ｄ）型の液晶ディスプレイでは、スイッチ液晶を利用した制御により表示画面の左右が異なる画像を見えるようにすることで実現されている。そのため、このような立体表示型の液晶ディスプレイのためには、より高速な応答速度を実現できるスイッチング素子が求められている。 By the way, in a liquid crystal display such as a flat-screen television, a display method has changed. Specifically, a liquid crystal display capable of stereoscopic display (3D) in addition to planar display (2D) is provided. This stereoscopic display (3D) type liquid crystal display is realized by making it possible to see different images on the left and right of the display screen by control using a switch liquid crystal. Therefore, for such a stereoscopic display type liquid crystal display, a switching element capable of realizing a higher response speed is required.
このような液晶ディスプレイの表示方式の変化に対応するべく、ＩＧＺＯのような酸化物型半導体材料の開発が種々行われている。高速な応答速度となるＴＦＴは、キャリア移動度が高いことが重要になる。例えば、ＩＧＺＯでは、ａ−Ｓｉに比べて１〜２桁も大きく、そのキャリア移動度は５〜１０ｃｍ２／Ｖｓ程度である。そのため、このＩＧＺＯであれば、立体表示型液晶ディスプレイのスイッチング素子であるＴＦＴの構成材料として使用可能であるが、よりハイスペックの液晶ディスプレイを実現するために、さらに高速な応答速度が実現できるＴＦＴの構成材料が要望されている。Various types of oxide semiconductor materials such as IGZO have been developed to cope with such changes in the display method of liquid crystal displays. It is important that a TFT having a high response speed has high carrier mobility. For example, in IGZO, it is 1 to 2 digits larger than a-Si, and its carrier mobility is about 5 to 10 cm 2 / Vs. Therefore, with this IGZO, it can be used as a constituent material of a TFT that is a switching element of a stereoscopic display type liquid crystal display, but in order to realize a higher spec liquid crystal display, a TFT capable of realizing a higher response speed. There are demands for constituent materials.
また、このＩＧＺＯは、ＴＦＴを形成する際に３５０℃以上のアニール処理を必要とするため、フレキシブル基板などを利用する有機ＥＬパネルや電子ペーパーのような高温熱処理ができない表示デバイスには利用することが困難である点が指摘されている。 In addition, this IGZO requires an annealing process of 350 ° C. or higher when forming a TFT, so it should be used for display devices that cannot be subjected to high-temperature heat treatment such as organic EL panels and electronic paper using a flexible substrate. It is pointed out that this is difficult.
さらに、資源的な問題や、人体や環境への影響から、ＩｎやＧａを用いない酸化物型半導体材料が要望されており、この点からのＩＧＺＯの代替材料の開発も必要とされている。 Furthermore, oxide-type semiconductor materials that do not use In or Ga are demanded due to resource problems and effects on the human body and the environment, and development of alternative materials for IGZO from this point is also required.
このＩＧＺＯの代替材料としては、例えば、Ｚｎ酸化物とＳｎ酸化物とからなる酸化物型半導体材料（ＺＴＯ：Ｚｎ−Ｓｎ−Ｏ系酸化物）が提案されている（特許文献２、特許文献３、特許文献４）。これら先行技術のＺＴＯは、高キャリア移動度を実現すべく開発されているが、ＴＦＴ形成時の熱処理温度の検討がされてなく、有機ＥＬパネルや電子ペーパーなどへの適用可能性が判明していない。そのため、ＩＧＺＯの代替材料としてのＺＴＯに関しても、更なる改善が求められているのが現状である。
As an alternative material for the IGZO, for example, an oxide semiconductor material (ZTO: Zn—Sn—O-based oxide) composed of Zn oxide and Sn oxide has been proposed (
本発明は、以上のような事情を背景になされたものであり、ＩＧＺＯの代替材料として、キャリア移動度がＩＧＺＯと同等以上のものとなり、１０ｃｍ２／Ｖｓ程度の高キャリア移動度で且つ、３００℃以上の高温熱処理を要しない、Ｚｎ酸化物とＳｎ酸化物とからなる酸化物型半導体材料（ＺＴＯ：Ｚｎ−Ｓｎ−Ｏ系酸化物）を提供することを目的とする。The present invention has been made in the background as described above. As an alternative material for IGZO, the carrier mobility is equal to or higher than that of IGZO, and has a high carrier mobility of about 10 cm 2 / Vs, and 300 An object of the present invention is to provide an oxide semiconductor material (ZTO: Zn—Sn—O-based oxide) composed of Zn oxide and Sn oxide, which does not require high-temperature heat treatment at a temperature of 0 ° C. or higher.
上記課題を解決すべく、本発明者等は、Ｚｎ酸化物とＳｎ酸化物とを含む酸化物型半導体材料に含有させるドーパントについて種々検討したところ、ある特定の元素をドーパントにすると、高キャリア移動度を有したまま、高温熱処理を要しなくても駆動するＴＦＴの作製が可能になるＺＴＯ膜になることを見出した。 In order to solve the above problems, the present inventors have studied various dopants to be included in an oxide semiconductor material containing Zn oxide and Sn oxide. When a specific element is used as a dopant, high carrier mobility is achieved. It has been found that the ZTO film can be manufactured without the need for high-temperature heat treatment while maintaining the degree.
本発明は、Ｚｎ酸化物とＳｎ酸化物とを含む酸化物型半導体材料であって、ドーパントとして、Ｍｇ（マグネシウム）、Ｃａ（カルシウム）、Ｌａ（ランタン）、Ｙ（イットリウム）のいずれか一種以上を含有し、ドーパント含有量は、金属元素としてのＺｎ（亜鉛）、Ｓｎ（スズ）、ドーパントの各原子数合計に対するドーパントの原子比が０．０９以下であることを特徴とする。 The present invention is an oxide semiconductor material containing Zn oxide and Sn oxide, and as a dopant, any one or more of Mg (magnesium), Ca (calcium), La (lanthanum), and Y (yttrium) The dopant content is characterized in that the atomic ratio of the dopant with respect to the total number of atoms of Zn (zinc), Sn (tin) as a metal element is 0.09 or less.
本発明に係る酸化物型半導体材料であれば、キャリア移動度がＩＧＺＯと同等以上のものとなり、１０ｃｍ２／Ｖｓ程度のキャリア移動度が実現でき、２５０℃以下の熱処理により、ＴＦＴなどのスイッチング素子を形成することが可能となる。また、Ｉｎ、Ｇａを含まないため、資源的な問題もなく、人体や環境への影響も少なくなる。With the oxide type semiconductor material according to the present invention, the carrier mobility is equal to or higher than that of IGZO, and carrier mobility of about 10 cm 2 / Vs can be realized. Can be formed. Moreover, since In and Ga are not included, there are no resource problems and the influence on the human body and the environment is reduced.
本発明の酸化物型半導体材料のドーパントは、Ｍｇ、Ｃａ、Ｌａ、Ｙのいずれか一種、或いは、これらを組み合わせて用いることができる。そして、このドーパントの含有量は、金属元素としてのＺｎ、Ｓｎ、ドーパントの各原子数合計に対するドーパントの原子比が０．０９以下とする。具体的には、金属元素としてのＺｎの原子数をｘ、Ｓｎの原子数をｙ、ドーパントの原子数をｚとした場合、ｚ／（ｘ＋ｙ＋ｚ）≦０．０９となるようにドーパントを含有させる。この原子比が、０．０９を超えると酸化物型半導体材料の抵抗値が大きくなり、半導体特性が得られなくなる。原子比が０．０９以下であると、キャリア密度が１×１０１８ｃｍ−３未満となるため、３５０℃熱処理後のＩＧＺＯ膜と同等以下のキャリア密度を実現できる。ドーパント含有量の下限値は、ＩＧＺＯと同等以下のキャリア密度を実現でき、２５０℃以下の熱処理によりＴＦＴなどのスイッチング素子を形成することができれば、その数値に制限はない。本発明者らの検討では、例えばＭｇの場合、ドーパント含有量が原子比で０．００１５であっても、本発明の酸化物型半導体材料として採用できることを確認している。そして、Ｍｇの場合、ドーパント含有量が原子比で０．０１未満であることが好ましい。０．０１未満であると、良好なＴＦＴ特性を実現しやすくなる。さらに、ドーパントがＣａの場合、そのドーパント含有量が原子比で０．０７４未満、ドーパントがＬａの場合、そのドーパント含有量が原子比で０．０２７未満、ドーパントがＹの場合、そのドーパント含有量が原子比で０．０３８未満であることが望ましい。尚、素子を形成する際のパターンニング特性については、ノンドープのＺＴＯ膜よりも、Ｍｇをドーパントとして用いたものの方が優れていることが確認された。The dopant of the oxide semiconductor material of the present invention can be any one of Mg, Ca, La, and Y, or a combination thereof. The dopant content is such that the atomic ratio of the dopant to the total number of atoms of Zn, Sn, and dopant as the metal elements is 0.09 or less. Specifically, the dopant is included so that z / (x + y + z) ≦ 0.09, where x is the number of Zn atoms as the metal element, y is the number of Sn atoms, and z is the number of dopant atoms. . When this atomic ratio exceeds 0.09, the resistance value of the oxide semiconductor material increases, and semiconductor characteristics cannot be obtained. When the atomic ratio is 0.09 or less, the carrier density is less than 1 × 10 18 cm −3 , so that a carrier density equivalent to or lower than that of the IGZO film after heat treatment at 350 ° C. can be realized. The lower limit of the dopant content is not limited as long as a carrier density equal to or lower than that of IGZO can be realized and a switching element such as a TFT can be formed by heat treatment at 250 ° C. or lower. In the study by the present inventors, for example, in the case of Mg, it has been confirmed that even if the dopant content is 0.0015 in atomic ratio, it can be adopted as the oxide semiconductor material of the present invention. And in the case of Mg, it is preferable that dopant content is less than 0.01 by atomic ratio. If it is less than 0.01, good TFT characteristics can be easily realized. Furthermore, when the dopant is Ca, the dopant content is less than 0.074 in atomic ratio, when the dopant is La, the dopant content is less than 0.027 in atomic ratio, and when the dopant is Y, the dopant content. Is preferably less than 0.038 in atomic ratio. Regarding the patterning characteristics when forming the element, it was confirmed that the one using Mg as a dopant was superior to the non-doped ZTO film.
本発明の酸化物型半導体材料は、ＺｎとＳｎとが、Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有していることが好ましく、０．６〜０．７の割合がより好ましい。このＡ／（Ａ＋Ｂ）が０．４未満になるとＳｎの比率が高くなるため、素子形成の際に成膜した薄膜をエッチングによりパターニングするときに、シュウ酸系エッチング液でのエッチングレートが極端に遅くなり、生産工程に適さなくなる。また、０．８を超えると、Ｚｎの比率が高くなるため、酸化物型半導体材料の水に対する耐性が低くなり、ＴＦＴ素子の形成の際に一般的に用いられる配線や半導体層のパターニング工程において、レジストの剥離液や純水洗浄の影響によりＺＴＯ膜そのものがダメージを受け、本来のＴＦＴ素子特性を実現できなくなり、場合によっては、ＺＴＯ膜が基板から溶解・脱落し、ＴＦＴ素子が形成できなくなる。 In the oxide semiconductor material of the present invention, Zn / Sn is A / (A + B) = 0.4 to 0, where A is the number of atoms of the metal element of Zn and B is the number of atoms of the metal element of Sn. It is preferable to contain in the ratio used as 0.8, and the ratio of 0.6-0.7 is more preferable. When the ratio A / (A + B) is less than 0.4, the Sn ratio increases. Therefore, when the thin film formed during element formation is patterned by etching, the etching rate with an oxalic acid-based etching solution is extremely high. Slow down and not suitable for production process. Further, when the ratio exceeds 0.8, the ratio of Zn increases, so the resistance of the oxide semiconductor material to water decreases, and in the patterning process of wiring and semiconductor layers generally used when forming TFT elements. The ZTO film itself is damaged by the influence of the resist stripping solution and pure water cleaning, and the original TFT element characteristics cannot be realized. In some cases, the ZTO film is dissolved and dropped from the substrate, and the TFT element cannot be formed. .
本発明において、ドーパントとしてＺｒをさらに含有させることもできる。Ｚｒ（ジルコニウム）も、本発明の酸化物型半導体材料のキャリア移動度を制御することに寄与できるからである。本発明において、ドーパントとして、Ｍｇ、Ｃａ、Ｌａ、Ｙのいずれか一種、或いは、これらを組み合わせて用い、さらにＺｒを含有する場合、Ｚｒの含有量は、材料中のすべてのドーパント総合計含有量が原子比で０．０９以下となるようにすることが好ましい。また、Ｚｒの含有量は、酸化物型半導体材料を構成する、金属元素としてのＺｎ（亜鉛）、Ｓｎ（スズ）、含有するすべてドーパントの各原子数合計に対するＺｒの原子比が０．００５以下とすることが好ましい。 In the present invention, Zr can be further contained as a dopant. This is because Zr (zirconium) can also contribute to controlling the carrier mobility of the oxide semiconductor material of the present invention. In the present invention, as a dopant, any one of Mg, Ca, La, and Y, or a combination thereof, and further containing Zr, the content of Zr is the total content of all dopants in the material. Is preferably 0.09 or less in atomic ratio. The Zr content is such that the atomic ratio of Zr to the total number of atoms of Zn (zinc), Sn (tin), and all the dopants constituting the oxide semiconductor material is 0.005 or less. It is preferable that
本発明の酸化物型半導体材料は、ボトムゲート型あるいはトップゲート型の薄膜トランジスタに非常に有効である。上記したように、本発明の酸化物型半導体材料であれば、ＩＧＺＯと同等以上のキャリア移動度が実現でき、２５０℃以下の低温熱処理で使用できるので、高い応答速度が要求される立体表示型の液晶ディスプレイに好適であり、フレキシブル基板などを利用する有機ＥＬパネルや電子ペーパーなどのスイッチング素子を形成する際にも適用することができる。 The oxide semiconductor material of the present invention is very effective for bottom-gate or top-gate thin film transistors. As described above, the oxide type semiconductor material of the present invention can realize carrier mobility equal to or higher than that of IGZO and can be used in low-temperature heat treatment at 250 ° C. or lower, so that a three-dimensional display type that requires a high response speed is required. It is suitable for a liquid crystal display, and can also be applied when forming a switching element such as an organic EL panel or electronic paper using a flexible substrate.
本発明の酸化物半導体材料によりスイッチング素子を形成する場合は、当該酸化物型半導体材料により形成された薄膜を利用することが有効であり、その薄膜を成膜するためにはスパッタ法を用いることが好ましい。 When the switching element is formed of the oxide semiconductor material of the present invention, it is effective to use a thin film formed of the oxide semiconductor material, and a sputtering method is used to form the thin film. Is preferred.
そして、このスパッタ法により本発明の酸化物型半導体材料の薄膜を成膜する際には、ドーパント含有量は、金属元素としてのＺｎ、Ｓｎ、ドーパントの各原子数合計に対するドーパントの原子比が０．０９以下であるスパッタリングターゲットを用いることが好ましい。そして、ＺｎとＳｎとは、Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有した合金ターゲットであることが好ましい。この場合、スパッタリングの成膜の際に、直流電源や高周波電源、パルスＤＣ電源を用いることができる。特に合金ターゲットを使用する場合には、パルスＤＣ電源を用いることで、ターゲット表面に発生するノジュールや表面高抵抗層の形成を抑制し、安定した成膜をすることが可能になるので、量産工程に適したものとなる。 When the thin film of the oxide semiconductor material of the present invention is formed by this sputtering method, the dopant content is such that the atomic ratio of the dopant to the total number of atoms of Zn, Sn, and dopant as metal elements is 0. It is preferable to use a sputtering target that is 0.09 or less. Zn and Sn are contained in a ratio of A / (A + B) = 0.4 to 0.8, where A is the number of atoms of the Zn metal element and B is the number of atoms of the Sn metal element. An alloy target is preferred. In this case, a direct-current power source, a high-frequency power source, or a pulsed DC power source can be used for film formation by sputtering. In particular, when using an alloy target, it is possible to suppress the formation of nodules and surface high resistance layers generated on the surface of the target by using a pulsed DC power source, and stable film formation is possible. It will be suitable for.
本発明の酸化物型半導体材料において、ドーパントとして、Ｚｒをさらに含有させる場合、Ｍｇ、Ｃａ、Ｌａ、Ｙのいずれか一種以上と、さらに、Ｚｒを所定量含有させたスパッタリングターゲットを用いることが好ましい。このようなスパッタリングターゲットを準備する場合には、目的組成の酸化物型半導体材料が成膜できるように、Ｚｎ酸化物とＳｎ酸化物と、Ｍｇ、Ｃａ、Ｌａ、Ｙのいずれか一種以上の酸化物と、Ｚｒ酸化物とを、混合して、焼結することによって製造できる。また、Ｚｎ酸化物とＳｎ酸化物と、Ｍｇ、Ｃａ、Ｌａ、Ｙのいずれか一種以上の酸化物とを、メディアとしてＺｒＯ２製ボールを用いた乾式ボールミルで混合処理することで、Ｚｒをさらに含有させることができる。このような乾式ボールミルによって、Ｚｒをドーパントとして混入することができるが、酸化物型半導体材料の均一性などを考慮すると、望ましくは、Ｚｒ酸化物を混合した方がよい。In the oxide semiconductor material of the present invention, when further containing Zr as a dopant, it is preferable to use a sputtering target containing at least one of Mg, Ca, La, and Y, and further containing a predetermined amount of Zr. . In the case of preparing such a sputtering target, Zn oxide, Sn oxide, and one or more kinds of oxides of Mg, Ca, La, and Y are formed so that an oxide semiconductor material having a target composition can be formed. And a Zr oxide can be mixed and sintered. Further, Zr can be further processed by mixing Zn oxide, Sn oxide, and one or more of Mg, Ca, La, and Y with a dry ball mill using a ZrO 2 ball as a medium. It can be included. Zr can be mixed as a dopant by such a dry ball mill. However, considering the uniformity of the oxide semiconductor material, it is preferable to mix Zr oxide.
本発明の酸化物型半導体材料を使って素子形成を行う場合には、上記スパッタ法により成膜することができるが、その他にもパルスレーザー蒸着法などスパッタ以外の成膜法を適応することもできる。また、半導体材料のナノ粒子が溶媒に分散した分散液を塗布する方法や、インクジェット法で回路形成することでも、本発明の酸化物型半導体材料を使った素子形成が可能である。 When element formation is performed using the oxide semiconductor material of the present invention, the film can be formed by the above sputtering method, but other film forming methods other than sputtering, such as pulsed laser deposition, can be applied. it can. Further, an element can be formed using the oxide semiconductor material of the present invention by applying a dispersion liquid in which nanoparticles of a semiconductor material are dispersed in a solvent or by forming a circuit by an ink jet method.
本発明の酸化物型半導体材料によれば、ＩＧＺＯと同等以上のキャリア移動度を実現でき、２５０℃以下の低温熱処理で、ＴＦＴなどのスイッチング素子を形成することが可能となる。また、Ｉｎ、Ｇａを含まないため、資源的な問題もなく、人体や環境への影響も低減することが可能となる。 According to the oxide semiconductor material of the present invention, carrier mobility equal to or higher than that of IGZO can be realized, and switching elements such as TFTs can be formed by low-temperature heat treatment at 250 ° C. or lower. In addition, since In and Ga are not included, there is no problem in terms of resources, and the influence on the human body and the environment can be reduced.
以下、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
第一実施形態：この第一実施形態においては、ドーパントとしてＭｇを用いた場合について説明する。 First Embodiment: In this first embodiment, a case where Mg is used as a dopant will be described.
まず、この第一実施形態の酸化物型半導体材料についてのスパッタリングターゲットの作製について説明する。
ターゲット作製：大気雰囲気中、５００℃で仮焼成を施したＺｎＯ粉と、大気雰囲気中、１０５０℃で仮焼成を施したＳｎＯ２粉と、仮焼していないＭｇＯ粉を各々所定量秤量し、樹脂製ポット（容量４Ｌ）に投入してボールミルにて混合した。このボールミルでは、回転数１３０ｒｐｍ、混合時間１２時間の混合を行った。そして、混合粉を目開き５００μｍ、線径３１５μｍの篩にて、ふるい分けを行った。粗粒分が取り除かれた篩下の混合粉を、φ１００ｍｍカーボン製プレス型に充填して、ホットプレスにより焼結体を作製した。ホットプレス条件は、Ａｒガス流量を３Ｌ/ｍｉｎとし、９．４ＭＰａ加圧下で１０５０℃まで昇温した後、２５ＭＰａ加圧下で９０分間保持し、自然冷却させ焼結体を取り出した。以上のような手順により、表１に示す各原子比となる薄膜を形成するための焼結体ターゲット形成をした。First, production of a sputtering target for the oxide semiconductor material of the first embodiment will be described.
Target preparation: ZnO powder subjected to preliminary firing at 500 ° C. in air atmosphere, SnO 2 powder subjected to preliminary firing at 1050 ° C. in air atmosphere, and MgO powder not subjected to preliminary firing are weighed in predetermined amounts, respectively. It put into the resin pot (capacity 4L) and mixed with the ball mill. In this ball mill, mixing was performed at a rotation speed of 130 rpm and a mixing time of 12 hours. The mixed powder was sieved with a sieve having an opening of 500 μm and a wire diameter of 315 μm. The mixed powder under the sieve from which the coarse particles were removed was filled into a φ100 mm carbon press die, and a sintered body was produced by hot pressing. The hot press conditions were such that the Ar gas flow rate was 3 L / min, the temperature was raised to 1050 ° C. under a pressure of 9.4 MPa, held for 90 minutes under a pressure of 25 MPa, naturally cooled, and the sintered body was taken out. The sintered compact target formation for forming the thin film which becomes each atomic ratio shown in Table 1 with the above procedures was performed.
次に、作製した焼結体ターゲットを用いたスパッタリングによる成膜方法、及びその膜評価について説明する。市販の枚様式スパッタリング装置（トッキ（株）製：ＳＭＬ−４６４）を用いて成膜した。スパッタリング条件は、到達真空度１×１０−５Ｐａとし、スパッタガスとしてＡｒ／Ｏ２混合ガスを用い、スパッタガス圧０．４Ｐａに設定し、酸素分圧０．０１Ｐａとして、室温（２５℃）のガラス基板（日本電気硝子（株）製：ＯＡ−１０）上に、１５０ＷのＤＣスパッタリングにより、約１００ｎｍ厚みの成膜を行った。Next, the film-forming method by sputtering using the produced sintered compact target, and the film | membrane evaluation are demonstrated. Film formation was performed using a commercially available sheet-type sputtering apparatus (manufactured by Tokki Co., Ltd .: SML-464). The sputtering conditions were an ultimate vacuum of 1 × 10 −5 Pa, an Ar / O 2 mixed gas as a sputtering gas, a sputtering gas pressure of 0.4 Pa, an oxygen partial pressure of 0.01 Pa, and room temperature (25 ° C.). A film having a thickness of about 100 nm was formed on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd .: OA-10) by DC sputtering of 150 W.
この成膜した膜組成は、ＩＣＰ（誘導結合プラズマ）発光分光分析装置（エスアイアイナノテクノロジー（株）製：Ｖｉｓｔａ Ｐｒｏ）を使用して行った。表１には、Ｚｎ、Ｓｎ、Ｍｇの測定値から、Ｚｎ／（Ｚｎ＋Ｓｎ）及び、Ｍｇ／（Ｚｎ＋Ｓｎ＋Ｍｇ）の原子比の値を算出して記載している。なお、薄膜トランジスタ（ＴＦＴ）などの素子に使用した場合、その酸化物型半導体材料の組成は、素子を切断し、その素子断面を透過型電子顕微鏡（ＴＥＭ）などで観察しながら、酸化物型半導体材料層を特定し、その部分をＥＤＸ分析することで特定することができる。 The film composition thus formed was performed using an ICP (inductively coupled plasma) emission spectroscopic analyzer (manufactured by SII Nano Technology Co., Ltd .: Vista Pro). Table 1 shows the values of the atomic ratios of Zn / (Zn + Sn) and Mg / (Zn + Sn + Mg) calculated from the measured values of Zn, Sn, and Mg. When used in an element such as a thin film transistor (TFT), the composition of the oxide semiconductor material is such that the oxide semiconductor is cut while the element is cut and observed through a transmission electron microscope (TEM) or the like. The material layer can be identified and the portion can be identified by EDX analysis.
そして、成膜した各試料を、大気雰囲気中、２００℃、３００℃で１時間アニール処理をして、それぞれホール効果測定を行い、各試料の比抵抗値、キャリア移動度、キャリア密度を求めた。このホール効果測定は、市販のホール効果測定装置（ナノメトリクス・ジャパン（株）製：ＨＬ５５００ＰＣ）により、１０ｍｍ×１０ｍｍ角に切り出した各試料を用いて行った。各試料の比抵抗値、キャリア移動度、キャリア密度の結果を表１に示す。 Then, each sample formed was annealed at 200 ° C. and 300 ° C. for 1 hour in the air atmosphere, and the Hall effect measurement was performed to determine the specific resistance value, carrier mobility, and carrier density of each sample. . This Hall effect measurement was performed using each sample cut into a 10 mm × 10 mm square by a commercially available Hall effect measuring device (manufactured by Nanometrics Japan Co., Ltd .: HL5500PC). Table 1 shows the results of the specific resistance value, carrier mobility, and carrier density of each sample.
ＴＦＴ評価：上記の膜をチャネル層とし、メタルマスクを用いて薄膜トランジスタ（ＴＦＴ）を作製した。図１には、形成したＴＦＴ素子の断面概略図（Ａ）及び平面寸法概略図（Ｂ）を示している。図１（Ａ）に示すように、ＴＦＴの形成は、まずはガラス基板１０上にゲート電極２０としてＡｌ合金（厚み２０００Å）を成膜した。ここでのスパッタガス圧は０．４Ｐａで、投入電力１０００ＷのＤＣスパッタを行った。次にゲート絶縁膜３０としてＳｉＮｘ（厚み３０００Å）を成膜した。ここではプラズマＣＶＤ装置（ｓａｍｃｏ社製：ＰＤ−２２０２Ｌ）により成膜を行い、基板温度３５０℃で投入電力２５０ＷのプラズマＣＶＤを行った。原料ガスの流量は、ＳｉＨ４：ＮＨ３：Ｎ２＝１００ｃｃ：１０ｃｃ：２００ｃｃとした。続いてチャネル層４０として上記ＺＴＯ−ＭｇＯ膜（厚み３００Å）を成膜した。ここでのスパッタガス圧は０．４Ｐａ、投入電力１５０ＷのＤＣスパッタを行った。チャネルのＷ／Ｌ＝２２とした。最後にソース電極５０（厚み２０００Å）とドレイン電極５１（厚み２０００Å）とを、ＩＴＯにより成膜した。ここでのスパッタガス圧は０．４Ｐａで、投入電力６００ＷのＤＣスパッタを行った。このようにして作製したＴＦＴの素子寸法について、図１（Ｂ）に示している。この図１（Ｂ）の各幅の数値単位はｍｍである。TFT evaluation: The above film was used as a channel layer, and a thin film transistor (TFT) was produced using a metal mask. FIG. 1 shows a schematic cross-sectional view (A) and a schematic plan view (B) of the formed TFT element. As shown in FIG. 1A, the TFT was formed by first forming an Al alloy (thickness: 2000 mm) on the
作製したＴＦＴについては、その伝達特性を半導体分析装置（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製Ｓｅｍｉｃｏｎｄｕｃｔｏｒ Ｄｅｖｉｃｅ Ａｎａｌｙｚｅｒ Ｂ１５００Ａ）により測定した。測定時に印加したドレイン電圧（Ｖｄｓ）は１〜５Ｖで、ゲート電圧（Ｖｇｓ）の測定幅は−１０〜２０Ｖとした。図２及び図３にＴＦＴの伝達特性を測定した結果を示す。図２がＺｎ／（Ｚｎ＋Ｓｎ）＝０．６６、Ｍｇ／（Ｚｎ＋Ｓｎ＋Ｍｇ）＝０．０１５の場合（実施例５、熱処理温度２００℃）であり、図３がＺｎ／（Ｚｎ＋Ｓｎ）＝０．６２、Ｍｇドーパント添加なしの場合（比較例４、熱処理温度２００℃）のＴＦＴ特性を示している。尚、図２及び３では、縦軸左側はドレイン電流：Ｉｄｓ（Ａ）値の対数軸であり、縦軸右側は√Ｉｄｓ値の小数点表示軸である。 About the produced TFT, the transmission characteristic was measured with the semiconductor analyzer (Semiconductor Device Analyzer B1500A by Agilent Technologies). The drain voltage (Vds) applied during the measurement was 1 to 5 V, and the measurement width of the gate voltage (Vgs) was −10 to 20 V. 2 and 3 show the results of measuring the transfer characteristics of the TFT. 2 shows the case where Zn / (Zn + Sn) = 0.66 and Mg / (Zn + Sn + Mg) = 0.015 (Example 5, heat treatment temperature 200 ° C.), and FIG. 3 shows Zn / (Zn + Sn) = 0.62. The TFT characteristics when no Mg dopant is added (Comparative Example 4, heat treatment temperature 200 ° C.) are shown. 2 and 3, the left side of the vertical axis is a logarithmic axis of drain current: Ids (A) value, and the right side of the vertical axis is a decimal point display axis of √Ids value.
表１に示すように、Ｍｇ含有量は、原子比０．００１５〜０．０７９であれば、２００℃熱処理後におけるスパッタ膜のキャリア密度は、１×１０１５ｃｍ−３以上１×１０１８ｃｍ−３未満の範囲に入ることが判明した。そして、図２に示すように、Ｚｎ／（Ｚｎ＋Ｓｎ）＝０．６６、Ｍｇ含有量が原子比で０．０１５（Ｍｇ／（Ｚｎ＋Ｓｎ＋Ｍｇ）：参考例６）の場合（キャリア密度４.７５×１０１６ｃｍ−３、そのＴＦＴ特性はｏｎ／ｏｆｆ比が５桁となり良好なＴＦＴ特性を示していることが判明した。このＴＦＴ特性を７個の素子で測定した結果、しきい値電圧Ｖｔｈ（Ｖ）が５．８８±１．９４Ｖ、電解効果移動度μ（ｃｍ２／Ｖｓ）が５．８４±０．５ｃｍ２／Ｖｓ、Ｓ値（Ｖ／ｄｅｃ）が１．０７±０．５Ｖ／ｄｅｃであった。一方、図３に示すように、Ｚｎ／（Ｚｎ＋Ｓｎ）＝０．６２、Ｍｇドーパント添加なしの場合（キャリア密度３．６２×１０１８ｃｍ−３）、そのＴＦＴ特性はｏｎ／ｏｆｆ比が２桁となり、この組成のＺＴＯ膜ではチャネル層としての機能が果たせないことが確認された。また、Ｍｇドーパント添加なしの素子についても、ＴＦＴ特性を７個の素子で測定した結果、そのうち５個の素子についてはｏｎ／ｏｆｆせずにｏｆｆしない素子となってしまい、残りの２個の素子では、しきい値電圧Ｖｔｈ（Ｖ）が−１２．９±２．３３Ｖ、電解効果移動度μ（ｃｍ２／Ｖｓ）が１３．７±３．５４ｃｍ２／Ｖｓ、Ｓ値（Ｖ／ｄｅｃ）が９．０７±２．４５Ｖ／ｄｅｃであった。尚、電解効果移動度μは、ＴＦＴ素子を形成してＴＦＴ特性を測定した結果より得られる値であり、表１のキャリア移動度は、成膜した膜のホール効果測定より得られた値である。また、Ｓ値とは、トランジスタの特性を示すサブスレッショルドスイング値（subthreshold swing value）である。
As shown in Table 1, when the Mg content is an atomic ratio of 0.0015 to 0.079, the carrier density of the sputtered film after heat treatment at 200 ° C. is 1 × 10 15 cm −3 or more and 1 × 10 18 cm. It was found to fall within the range of less than -3 . As shown in FIG. 2, when Zn / (Zn + Sn) = 0.66 and the Mg content is 0.015 (Mg / (Zn + Sn + Mg): Reference Example 6 ) in atomic ratio (carrier density 4.75 × 10 It was found that the TFT characteristic was 16 cm −3 , and the on / off ratio was 5 digits, indicating good TFT characteristics, and the TFT characteristics were measured with seven elements, and as a result, the threshold voltage Vth (V ) Is 5.88 ± 1.94V, electrolysis effect mobility μ (cm 2 / Vs) is 5.84 ± 0.5 cm 2 / Vs, and S value (V / dec) is 1.07 ± 0.5 V / dec. On the other hand, as shown in Fig. 3, when Zn / (Zn + Sn) = 0.62 and no Mg dopant was added (carrier density 3.62 × 10 18 cm −3 ), the TFT characteristics were on / off. ZTO film with this composition As a result of measuring TFT characteristics with 7 elements, it was confirmed that 5 elements were not turned on / off. In the remaining two elements, the threshold voltage Vth (V) is −12.9 ± 2.33 V, and the field effect mobility μ (cm 2 / Vs) is 13.7. ± 3.54 cm 2 / Vs, S value (V / dec) was 9.07 ± 2.45 V / dec Electrolytic effect mobility μ is a result of measuring TFT characteristics after forming TFT elements. The carrier mobility in Table 1 is a value obtained by measuring the Hall effect of the deposited film, and the S value is a subthreshold swing value indicating the characteristics of the transistor. value) .
さらに、図４に示すように、Ｚｎ／（Ｚｎ＋Ｓｎ）＝０．６６、Ｍｇ含有量が原子比で０．００９（Ｍｇ／（Ｚｎ＋Ｓｎ＋Ｍｇ）：実施例５）の場合（キャリア密度５．９０×１０１６ｃｍ−３、そのＴＦＴ特性はｏｎ／ｏｆｆ比が５桁となり良好なＴＦＴ特性を示していることが確認された。このＴＦＴ特性を７個の素子で測定した結果、しきい値電圧Ｖｔｈ（Ｖ）が０．４３±０．４２Ｖ、電解効果移動度μ（ｃｍ２／Ｖｓ）が６．０２±０．６３ｃｍ２／Ｖｓ、Ｓ値（Ｖ／ｄｅｃ）が０．７３±０．３Ｖ／ｄｅｃであった。また、参考例８も同様にＴＦＴ特性を調べたところ、作製した７個のうち特性を示した１個の素子で測定した結果では、しきい値電圧Ｖｔｈ（Ｖ）が５．７５Ｖ、電解効果移動度μ（ｃｍ２／Ｖｓ）が０．７０ｃｍ２／Ｖｓ、Ｓ値（Ｖ／ｄｅｃ）が０．８５Ｖ／ｄｅｃであった。このＴＦＴ特性の結果について、実施例５、参考例６、参考例８を比較すると、実施例５（Ｍｇ含有量が原子比で０．００９（Ｍｇ／（Ｚｎ＋Ｓｎ＋Ｍｇ））のＴＦＴが非常に良好なＴＦＴ特性であることが判明した。 Furthermore, as shown in FIG. 4, when Zn / (Zn + Sn) = 0.66 and the Mg content is 0.009 in terms of atomic ratio (Mg / (Zn + Sn + Mg): Example 5) (carrier density 5.90 × 10 It was confirmed that the TFT characteristic was 16 cm −3 , and the on / off ratio was 5 digits, indicating that the TFT characteristic was good, and the TFT characteristic was measured with seven elements. V) is 0.43 ± 0.42 V, the electrolytic effect mobility μ (cm 2 / Vs) is 6.02 ± 0.63 cm 2 / Vs, and the S value (V / dec) is 0.73 ± 0.3 V / In addition, when the TFT characteristics were similarly examined in Reference Example 8 , the threshold voltage Vth (V) was 5 as a result of measurement with one of the seven manufactured elements exhibiting the characteristics. .75V, electrolysis effect mobility μ (cm2 / Vs) is 0.70 m @ 2 / Vs, S value (V / dec) was 0.85V / dec. The results of this TFT characteristics, Example 5, Reference Example 6, a comparison of Example 8, Example 5 (Mg content It was found that a TFT having an atomic ratio of 0.009 (Mg / (Zn + Sn + Mg)) has very good TFT characteristics.
第二実施形態：この第二実施形態においては、ドーパントして、Ｃａ、Ｌａ、Ｙを用いた場合について説明する。 Second Embodiment: In this second embodiment, a case where Ca, La, and Y are used as dopants will be described.
これらのドーパントを用いたターゲットについては、第一実施形態の場合と同様な方法により作製し、表２に示した組成の成膜を行った。表２には、Ｚｎ、Ｓｎ、ドーパント（Ｃａ、Ｌａ、Ｙ）の測定値から、Ｚｎ／（Ｚｎ＋Ｓｎ）及び、ドーパント／（Ｚｎ＋Ｓｎ＋ドーパント）の原子比の値を算出して記載している。また、成膜条件、比抵抗値、キャリア移動度、キャリア密度の測定については、第一実施形態と同様である。その結果を表２に示す。 About the target using these dopants, it produced by the method similar to the case of 1st embodiment, and formed into a film with the composition shown in Table 2. In Table 2, the atomic ratio values of Zn / (Zn + Sn) and dopant / (Zn + Sn + dopant) are calculated from the measured values of Zn, Sn, and dopants (Ca, La, Y). In addition, the film forming conditions, specific resistance value, carrier mobility, and carrier density are measured in the same manner as in the first embodiment. The results are shown in Table 2.
表２に示すように、ドーパントとしてＣａ、Ｌａ、Ｙを用いたＺＴＯ膜は、２００℃の熱処理であっても、比抵抗値は実用上問題なく、キャリア密度も１０１５ｃｍ−３以上１０１８ｃｍ−３未満の範囲に入るものであることが判明した。また、これの組成によるＴＦＴ特性も、ｏｎ／ｏｆｆ比が５桁となる良好な結果が得られた。As shown in Table 2, the ZTO film using Ca, La, and Y as dopants has no practical problem in the specific resistance value even when heat-treated at 200 ° C., and the carrier density is 10 15 cm −3 or more and 10 18. It was found to fall within the range of less than cm −3 . Moreover, the TFT characteristic by this composition also showed a favorable result with an on / off ratio of 5 digits.
また、図５に示すように、Ｚｎ／（Ｚｎ＋Ｓｎ）＝０．６６、Ｃａ含有量が原子比で０．００３（Ｃａ／（Ｚｎ＋Ｓｎ＋Ｃａ）：実施例１２）の場合（キャリア密度５．１０×１０１６ｃｍ−３、そのＴＦＴ特性はｏｎ／ｏｆｆ比が５桁となり良好なＴＦＴ特性を示していることが判明した。このＴＦＴ特性を７個の素子のうちの４個で測定した結果、しきい値電圧Ｖｔｈ（Ｖ）が１．９９±０．８３Ｖ、電解効果移動度μ（ｃｍ２／Ｖｓ）が５．２０±０．７２ｃｍ２／Ｖｓ、Ｓ値（Ｖ／ｄｅｃ）が０．５５±０．０８Ｖ／ｄｅｃであった。Further, as shown in FIG. 5, when Zn / (Zn + Sn) = 0.66 and the Ca content is 0.003 (Ca / (Zn + Sn + Ca): Example 12) in terms of atomic ratio (carrier density 5.10 × 10 6 It was found that the TFT characteristic was 16 cm −3 , and the on / off ratio was 5 digits, indicating good TFT characteristics, and the TFT characteristics were measured with four of the seven elements. Value voltage Vth (V) is 1.99 ± 0.83 V, field effect mobility μ (cm 2 / Vs) is 5.20 ± 0.72 cm 2 / Vs, and S value (V / dec) is 0.55 ±. It was 0.08V / dec.
第三実施形態：この第三実施形態においては、ドーパントして、ＭｇとＺｒを用いた場合について説明する。 Third Embodiment: In this third embodiment, a case where Mg and Zr are used as dopants will be described.
このＭｇとＺｒをドーパントとして用いたターゲットについては、第一実施形態の場合と同様に、大気雰囲気中５００℃で仮焼成を施したＺｎＯ粉と、大気雰囲気中１０５０℃で仮焼成を施したＳｎＯ２粉と、仮焼していないＭｇＯ粉及びＺｒＯ２粉を各々所定量秤量し、ボールミルにて混合した（混合条件は第一実施形態と同様）。そして、ふるい分け処理、ホットプレスにより焼結体を作製した（ふるい分け処理、ホットプレス条件は第一実施形態と同様）。そして、この焼結体をスパッタリングターゲットを用い、表３に示した組成の成膜を行った。表３には、Ｚｎ、Ｓｎ、ドーパント（Ｍｇ、Ｚｒ）の測定値から、Ｚｎ／（Ｚｎ＋Ｓｎ）及び、（Ｍｇ＋Ｚｒ）／（Ｚｎ＋Ｓｎ＋Ｚｒ＋Ｍｇ）の原子比の値を算出して記載している。また、成膜条件、比抵抗値、キャリア移動度、キャリア密度の測定については、第一実施形態と同様である。その結果を表３に示す。As for the target using Mg and Zr as dopants, similarly to the case of the first embodiment, ZnO powder preliminarily calcined at 500 ° C. in the air atmosphere and SnO calcined at 1050 ° C. in the air atmosphere. Two powders, uncalcined MgO powder and ZrO 2 powder were weighed in predetermined amounts and mixed in a ball mill (mixing conditions were the same as in the first embodiment). And the sintered compact was produced by the sieving process and hot press (the sieving process and hot press conditions are the same as that of 1st embodiment). Then, a film having the composition shown in Table 3 was formed on the sintered body using a sputtering target. Table 3 shows the values of the atomic ratios of Zn / (Zn + Sn) and (Mg + Zr) / (Zn + Sn + Zr + Mg) calculated from the measured values of Zn, Sn, and dopants (Mg, Zr). In addition, the film forming conditions, specific resistance value, carrier mobility, and carrier density are measured in the same manner as in the first embodiment. The results are shown in Table 3.
表３に示すように、ドーパントとしてＭｇ及びＺｒ（Ｍｇドーパントは原子比（Ｍｇ／（Ｚｎ＋Ｓｎ＋Ｚｒ＋Ｍｇ））で０．００００８４９、Ｚｒドーパントは原子比（Ｚｒ／（Ｚｎ＋Ｓｎ＋Ｚｒ＋Ｍｇ））で０．００１２、よってトータル含有量の原子比が０．００１２８４９）を用いたＺＴＯ膜は、２００℃の熱処理であっても、比抵抗値は実用上問題なく、キャリア密度も１０１５ｃｍ−３以上１０１８ｃｍ−３未満の範囲に入るものであることが判明した。また、これの組成によるＴＦＴ特性も、ｏｎ／ｏｆｆ比が５桁以上となる良好な結果が得られた。As shown in Table 3, Mg and Zr as dopants (Mg dopant is atomic ratio (Mg / (Zn + Sn + Zr + Mg)) is 0.0000849, Zr dopant is atomic ratio (Zr / (Zn + Sn + Zr + Mg)) is 0.0012, and thus total content A ZTO film using a quantity atomic ratio of 0.0012849) has a practically no specific resistance value and a carrier density of 10 15 cm −3 or more and less than 10 18 cm −3 even when heat treatment at 200 ° C. It turned out to be in range. Moreover, the TFT characteristic by this composition also showed a favorable result that the on / off ratio was 5 digits or more.
また、ターゲットの製造において、ＺｒＯ２製ボールによる乾式ボールミルによって混合処理をすることで、酸化物型半導体材料のＺｒ含有量の変化を調べた。具体的には、上記実施例１７の場合と同様に、所定量のＺｎＯ粉、ＳｎＯ２粉、ＭｇＯ粉を、ＺｒＯ２製ボールによる乾式ボールミルにより混合処理を行い、焼結体を形成した（混合条件、ふるい分け処理、ホットプレス条件は同じ）。その結果、混合処理を１２時間行ったところ、成膜した酸化物型半導体材料のＺｒ含有量は、原子比で０．００００４６であり、２０時間の場合０．００００６３であることが判明した。そして、このＺｒＯ２製ボールによりＺｒを含有させた酸化物型半導体材料においても、その電子特性は実施例１７と同様であることが確認された。Further, in the production of the target, a change in the Zr content of the oxide semiconductor material was examined by performing a mixing process using a dry ball mill using ZrO 2 balls. Specifically, as in the case of Example 17, a predetermined amount of ZnO powder, SnO 2 powder, and MgO powder were mixed by a dry ball mill using ZrO 2 balls to form a sintered body (mixed) Conditions, sifting process, and hot press conditions are the same). As a result, when the mixing process was performed for 12 hours, it was found that the Zr content of the deposited oxide semiconductor material was 0.000046 in terms of atomic ratio and 0.000063 in the case of 20 hours. It was confirmed that the electronic characteristics of the oxide semiconductor material containing Zr by the ZrO 2 balls were the same as those in Example 17.
本発明の酸化物型半導体材料は、立体表示型液晶ディスプレイのスイッチング素子のような、より高速な応答速度が要求されるＴＦＴの構成材料として極めて有効である。また、本発明の酸化物型半導体材料は、低温熱処理で使用可能なため、フレキシブル基板などを利用する有機ＥＬパネルや電子ペーパーに好適であり、資源的な問題や人体や環境への影響の観点からも産業上の利用価値が高い。 The oxide semiconductor material of the present invention is extremely effective as a constituent material of a TFT that requires a higher response speed, such as a switching element of a stereoscopic display type liquid crystal display. In addition, since the oxide semiconductor material of the present invention can be used in low-temperature heat treatment, it is suitable for organic EL panels and electronic papers that use flexible substrates, etc., and has a viewpoint of resource problems and effects on human bodies and the environment. Therefore, the industrial utility value is high.
Claims (14)
Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有し、さらにドーパントとして、Ｍｇを含有し、ドーパント含有量は、Ｚｎの金属元素の原子数をｘ、Ｓｎの金属元素の原子数をｙ、Ｍｇの金属元素の原子数ｚとした場合、ｚ／（ｘ＋ｙ＋ｚ）＜０．０１であることを特徴とする酸化物型半導体材料。 An oxide type semiconductor material containing Zn oxide and Sn oxide,
When the number of atoms of the metal element of Zn is A and the number of atoms of the Sn metal element is B, it is contained at a ratio of A / (A + B) = 0.4 to 0.8, and further contains Mg as a dopant. The dopant content is z / (x + y + z) <0.01, where x is the number of atoms of the Zn metal element, y is the number of atoms of the Sn metal element, and z is the number of atoms of the Mg metal element. An oxide semiconductor material characterized by the above.
Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有し、さらにドーパントとして、Ｃａを含有し、ドーパント含有量は、Ｚｎの金属元素の原子数をｘ、Ｓｎの金属元素の原子数をｙ、Ｃａの金属元素の原子数ｚとした場合、ｚ／（ｘ＋ｙ＋ｚ）≦０．０９であることを特徴とする酸化物型半導体材料。 An oxide type semiconductor material containing Zn oxide and Sn oxide,
When the number of atoms of the metal element of Zn is A and the number of atoms of the Sn metal element is B, it is contained at a ratio of A / (A + B) = 0.4 to 0.8, and further contains Ca as a dopant. The dopant content is z / (x + y + z) ≦ 0.09, where x is the number of atoms of the Zn metal element, y is the number of atoms of the Sn metal element, and z is the number of atoms of the Ca metal element. An oxide semiconductor material characterized by the above.
Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有し、さらにドーパントとして、Ｍｇ、Ｃａ、Ｌａ、Ｙのいずれか一種以上を含有し、さらにドーパントとしてＺｒを含有し、ドーパント含有量は、Ｚｎの金属元素の原子数をｘ、Ｓｎの金属元素の原子数をｙ、ドーパントの金属元素の各原子数合計をｚとした場合、ｚ／（ｘ＋ｙ＋ｚ）≦０．０９であり、またＺｒのドーパント量は、金属元素としてのＺｎ、Ｓｎ、含有するすべてのドーパントの各原子数合計に対するＺｒの原子比が０．００５以下であることを特徴とする酸化物型半導体材料。 An oxide type semiconductor material containing Zn oxide and Sn oxide,
When the number of atoms of the metal element of Zn is A and the number of atoms of the Sn metal element is B, it is contained at a ratio of A / (A + B) = 0.4 to 0.8, and further, Mg, Ca as dopants , La, and Y, and further contains Zr as a dopant. The dopant content is x for the number of atoms of the Zn metal element, y for the number of atoms of the Sn metal element, and the metal element of the dopant. Z / (x + y + z) ≦ 0.09, and the amount of the Zr dopant is Zr relative to the total number of atoms of Zn, Sn, and all the contained dopants. An oxide semiconductor material characterized in that the atomic ratio of is 0.005 or less.
Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有し、さらにドーパントとして、Ｍｇを含有し、さらにドーパントとしてＺｒを含有し、ドーパント含有量は、Ｚｎの金属元素の原子数をｘ、Ｓｎの金属元素の原子数をｙ、Ｍｇの金属元素の原子数ｚとした場合、ｚ／（ｘ＋ｙ＋ｚ）≦０．０２１であり、またＺｒのドーパント量は、金属元素としてのＺｎ、Ｓｎ、含有するすべてのドーパントの各原子数合計に対するＺｒの原子比が０．００５以下であることを特徴とする酸化物型半導体材料。 An oxide type semiconductor material containing Zn oxide and Sn oxide,
When the number of atoms of the metal element of Zn is A and the number of atoms of the Sn metal element is B, it is contained at a ratio of A / (A + B) = 0.4 to 0.8, and further contains Mg as a dopant. Further, when Zr is contained as a dopant, the dopant content is z / (when the number of atoms of the Zn metal element is x, the number of atoms of the Sn metal element is y, and the number of atoms of the Mg metal element is z. x + y + z) ≦ 0.021, and the amount of Zr dopant is characterized in that the atomic ratio of Zr to the total number of atoms of Zn, Sn, and all the dopants contained in the metal element is 0.005 or less. Oxide-type semiconductor material.
Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有し、さらにドーパントとして、Ｃａを含有し、さらにドーパントとしてＺｒを含有し、ドーパント含有量は、Ｚｎの金属元素の原子数をｘ、Ｓｎの金属元素の原子数をｙ、Ｃａの金属元素の原子数ｚとした場合、ｚ／（ｘ＋ｙ＋ｚ）≦０．０９であり、またＺｒのドーパント量は、金属元素としてのＺｎ、Ｓｎ、含有するすべてのドーパントの各原子数合計に対するＺｒの原子比が０．００５以下であることを特徴とする酸化物型半導体材料。 An oxide type semiconductor material containing Zn oxide and Sn oxide,
When the number of atoms of the metal element of Zn is A and the number of atoms of the Sn metal element is B, it is contained at a ratio of A / (A + B) = 0.4 to 0.8, and further contains Ca as a dopant. In addition, Zr is contained as a dopant, and the dopant content is z / (when the number of atoms of the Zn metal element is x, the number of atoms of the Sn metal element is y, and the number of atoms of the Ca metal element is z. x + y + z) ≦ 0.09, and the amount of Zr dopant is characterized in that the atomic ratio of Zr to the total number of atoms of Zn, Sn, and all the dopants contained in the metal element is 0.005 or less. Oxide-type semiconductor material.
Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有し、さらにドーパントとして、Ｌａを含有し、さらにドーパントとしてＺｒを含有し、ドーパント含有量は、Ｚｎの金属元素の原子数をｘ、Ｓｎの金属元素の原子数をｙ、Ｌａの金属元素の原子数ｚとした場合、ｚ／（ｘ＋ｙ＋ｚ）≦０．０１２９であり、またＺｒのドーパント量は、金属元素としてのＺｎ、Ｓｎ、含有するすべてのドーパントの各原子数合計に対するＺｒの原子比が０．００５以下であることを特徴とする酸化物型半導体材料。 An oxide type semiconductor material containing Zn oxide and Sn oxide,
When the number of atoms of the metal element of Zn is A and the number of atoms of the Sn metal element is B, it is contained at a ratio of A / (A + B) = 0.4 to 0.8, and further contains La as a dopant. Further, when Zr is contained as a dopant and the dopant content is x, the number of atoms of the Zn metal element is y, the number of atoms of the Sn metal element is y, and the number of atoms z of the La metal element is z / ( x + y + z) ≦ 0.0129, and the amount of Zr dopant is characterized in that the atomic ratio of Zr to the total number of atoms of Zn, Sn, and all the dopants contained in the metal element is 0.005 or less. Oxide-type semiconductor material.
Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有し、さらにドーパントとして、Ｙを含有し、さらにドーパントとしてＺｒを含有しドーパント含有量は、Ｚｎの金属元素の原子数をｘ、Ｓｎの金属元素の原子数をｙ、Ｙの金属元素の原子数ｚとした場合、ｚ／（ｘ＋ｙ＋ｚ）＜０．０３８あり、またＺｒのドーパント量は、金属元素としてのＺｎ、Ｓｎ、含有するすべてのドーパントの各原子数合計に対するＺｒの原子比が０．００５以下であることを特徴とする酸化物型半導体材料。 An oxide type semiconductor material containing Zn oxide and Sn oxide,
When the number of atoms of the metal element of Zn is A and the number of atoms of the metal element of Sn is B, it is contained at a ratio of A / (A + B) = 0.4 to 0.8, and further contains Y as a dopant. Zr is further contained as a dopant, and the dopant content is expressed as z / (x + y + z) where x is the number of atoms of the Zn metal element, y is the number of atoms of the Sn metal element, and z is the number of atoms of the Y metal element. ) <0.038, and the amount of Zr dopant is such that the atomic ratio of Zr to the total number of atoms of Zn, Sn, and all dopants contained is 0.005 or less. Physical semiconductor material.
Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有し、さらにドーパントとして、Ｍｇを含有し、ドーパント含有量は、Ｚｎの金属元素の原子数をｘ、Ｓｎの金属元素の原子数をｙ、Ｍｇの原子数ｚとした場合、ｚ／（ｘ＋ｙ＋ｚ）＜０．０１であることを特徴とするスパッタリングターゲット。 Containing Zn oxide and Sn oxide,
When the number of atoms of the metal element of Zn is A and the number of atoms of the Sn metal element is B, it is contained at a ratio of A / (A + B) = 0.4 to 0.8, and further contains Mg as a dopant. The dopant content is z / (x + y + z) <0.01, where x is the number of atoms of the Zn metal element, y is the number of atoms of the Sn metal element, and z is the number of Mg atoms. Sputtering target.
Ｚｎの金属元素の原子数をＡ、Ｓｎの金属元素の原子数をＢとした場合、Ａ／（Ａ＋Ｂ）＝０．４〜０．８となる割合で含有し、さらにドーパントとして、Ｃａを含有し、ドーパント含有量は、Ｚｎの金属元素の原子数をｘ、Ｓｎの金属元素の原子数をｙ、Ｃａの原子数ｚとした場合、ｚ／（ｘ＋ｙ＋ｚ）≦０．０９であることを特徴とするスパッタリングターゲット。 Containing Zn oxide and Sn oxide,
When the number of atoms of the metal element of Zn is A and the number of atoms of the Sn metal element is B, it is contained at a ratio of A / (A + B) = 0.4 to 0.8, and further contains Ca as a dopant. The dopant content is z / (x + y + z) ≦ 0.09, where x is the number of atoms of the metal element of Zn, y is the number of atoms of the metal element of Sn, and z is the number of atoms of Ca. Sputtering target.
A ratio of A / (A + B) = 0.4 to 0.8, where Zn oxide and Sn oxide are included, the number of atoms of Zn metal element is A and the number of atoms of Sn metal element is B In addition, Y is contained as a dopant, Zr is further contained as a dopant, and the dopant content is such that the number of atoms of the Zn metal element is x, the number of atoms of the Sn metal element is y, and the number of atoms of the Y metal element is When the number of atoms is z, z / (x + y + z) <0.038, and the amount of Zr dopant is such that the atomic ratio of Zr with respect to the total number of atoms of Zn, Sn, and all dopants contained as metal elements is 0. 0.005 or less, sputtering target characterized by the above-mentioned.
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