Noncrystalline oxide semiconductor thin film, process for producing the noncrystalline oxide semiconductor thin film, process for producing thin-film transistor, field-effect-transistor, light emitting device, display device, and sputtering target

• US 8,232,552 B2
• Filed: 03/26/2008
• Issued: 07/31/2012
• Est. Priority Date: 03/26/2007
• Status: Active Grant

• Current Assignee: Idemitsu Kosan Company Limited
• Original Assignee: Idemitsu Kosan Company Limited
• Inventors: Yano, Koki, Inoue, Kazuyoshi
• Primary Examiner(s): HO, TU TU V
• Application Number:
  US12/593,045
• Publication Number:
  US 20100155717A1
• Time in Patent Office: 1,588 Days
• Field of Search: 257/43, 257/59, 257/347, 257/E29.101, 257/E29.273, 257/E21.471, 257/E21.497, 438/104, 438/34, 438/796
• US Class Current: 257/43
• CPC Class Codes: C04B 2235/3224 Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
• CPC Class Codes: C04B 2235/3227 Lanthanum oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3229 Cerium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3284 Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
• CPC Class Codes: C04B 2235/3286 Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
• CPC Class Codes: C04B 2235/3293 Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
• CPC Class Codes: C04B 2235/6562 Heating rate
• CPC Class Codes: C04B 2235/77 Density
• CPC Class Codes: C04B 35/453 based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
• CPC Class Codes: C04B 35/6261 Milling
• CPC Class Codes: C23C 14/086 of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• CPC Class Codes: C23C 14/3414 Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
• CPC Class Codes: C23C 14/3492 Variation of parameters during sputtering
• CPC Class Codes: H01L 21/02554 Oxides
• CPC Class Codes: H01L 21/02565 Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
• CPC Class Codes: H01L 21/02592 amorphous
• CPC Class Codes: H01L 21/02631 Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
• CPC Class Codes: H01L 21/32134 by liquid etching only
• CPC Class Codes: H01L 27/1225 with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
• CPC Class Codes: H01L 29/45 Ohmic electrodes
• CPC Class Codes: H01L 29/66969 : of devices having semiconductor bodies not comprising group 14 or group 13/15 materials comprising selenium or tellurium in uncombined form other than as impurities in semiconductor bodies of other materials, comprising cuprous oxide or cuprous iodide H01L21/02365
• CPC Class Codes: H01L 29/7869 : having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate

Abstract

This invention provides an amorphous oxide semiconductor thin film, which is insoluble in a phosphoric acid-based etching solution and is soluble in an oxalic acid-based etching solution by optimizing the amounts of indium, tin, and zinc, a method of producing the amorphous oxide semiconductor thin film, etc. An image display device (1) comprises a glass substrate (10), a liquid crystal (40) as a light control element, a bottom gate-type thin film transistor (1) for driving the liquid crystal (40), a pixel electrode (30), and an opposing electrode (50). The amorphous oxide semiconductor thin film (2) in the bottom gate-type thin film transistor (1) has a carrier density of less than 10⁺¹⁸ cm⁻³, is insoluble in a phosphoric acid-based etching liquid, and is soluble in an oxalic acid-based etching liquid.

Claims

1. An amorphous oxide semiconductor thin film having a carrier density of less than 10⁺¹⁸ cm⁻

3, and being insoluble in a phosphoric acid-based etching solution and soluble in an oxalic acid-based etching solution.

2. The amorphous oxide semiconductor thin film according to claim 1, wherein the etching rate in a phosphoric acid-based etching solution at 35°

C. is less than 10 nm/min, and the etching rate in an oxalic acid-based etching solution at 35°

C. is 20 nm/min or more.

3. The amorphous oxide semiconductor thin film according to claim 1, which comprises indium, tin, zinc and oxygen, and wherein when an atomic ratio of the number of tin atoms ([Sn]), relative to the sum of the number of indium atoms ([In]), the number of tin atoms ([Sn]) and the number of zinc atoms ([Zn]) is more than 0.1 and less than 0.2, the atomic ratio 1 below is satisfied, and when the atomic ratio of the [Sn] is 0.2 or more and less than 0.3, the atomic ratio 2 below is satisfied:

Atomic Ratio 1

0.1<

[In]/([In]+[Sn]+[Zn])<

0.5

0.1<

[Sn]/([In]+[Sn]+[Zn])<

0.2

0.3<

[Zn]/([In]+[Sn]+[Zn])<

0.8

Atomic Ratio 2

0.01<

[In]/([In]+[Sn]+[Zn])<

0.3

0.2[Sn]/([In]+[Sn]+[Zn])<

0.3

0.4<

[Zn]/([In]+[Sn]+[Zn])<

0.8.

4. The amorphous oxide semiconductor thin film according to claim 3, wherein an atomic ratio of the [Sn] relative to the sum of the [Sn] and [Zn] is

0.1<

[Sn]/([Sn]+[Zn])<

0.3.

5. The amorphous oxide semiconductor thin film according to claim 3, which comprises a IIIB group element other than indium (at least one of B, Al, Ga and Tl), and wherein an atomic ratio of the number of atoms of the IIIB group element ([IIIB]) relative to the sum of the [In], [Sn], [Zn] and [IIIB] is

0.0001<

[IIIB]/([In]+[Sn]+[Zn]+[IIIB])<

0.33.

6. The amorphous oxide semiconductor thin film according to claim 3, which comprises a lanthanoid series element (at least one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu), and wherein an atomic ratio of the number of atoms of the lanthanoid series element ([Ln]) relative to the sum of the [In], [Sn], [Zn] and [Ln] is

0.0001<

[Ln]/([In]+[Sn]+[Zn]+[Ln])<

0.1.

7. A method of producing an amorphous oxide semiconductor thin film according to claim 1, which comprises steps of:

forming an amorphous oxide semiconductor thin film having a carrier density of 10⁺¹⁸ cm<sup>−

3</sup> or more under a condition of the temperature of a substrate being lower than 150°

C., and

adjusting the carrier density to less than 10⁺¹⁸ cm<sup>−

3</sup> by applying a treatment to increase resistance to the amorphous thin film.

8. The method of producing an amorphous oxide semiconductor thin film according to claim 7, wherein the treatment to increase resistance is a heat treatment conducted under conditions of at 150 to 650°

C. for 0.5 to 12,000 minutes in the presence of oxygen.

9. A method of producing a thin film transistor using an amorphous oxide semiconductor thin film according to claim 1, as an active layer, which comprises steps of:

forming the active layer by etching the active layer using the amorphous oxide semiconductor thin film with an etching solution containing a carboxylic acid, and

forming an electrode layer by etching the electrode layer disposed upward the active layer with an etching solution containing an oxo acid.

10. A field-effect type transistor using an amorphous oxide semiconductor thin film according to claim 1, as an active layer.

11. The field-effect type transistor according to claim 10, wherein the amorphous oxide semiconductor thin film is etched with an etching solution containing a carboxylic acid, and an electrode etched with an etching solution containing an oxo acid is provided on the amorphous oxide semiconductor thin film.

12. The field-effect type transistor according to claim 10, wherein the amorphous oxide semiconductor thin film varies in the composition in the direction of film thickness and has a first region far from a gate insulating film and a second region near the gate insulating film, and the oxygen concentration in the second region is higher than the oxygen concentration in the first region.

13. The field-effect type transistor according to claim 10, wherein the amorphous oxide semiconductor thin film varies in the composition in the direction of film thickness and has a first region far from a gate insulating film and a second region near the gate insulating film, and the Sn concentration in the second region is lower than the Sn concentration in the first region.

14. A light emitting apparatus comprising

a light control element, and

a field-effect type transistor according to claim 10, for driving the light control element.

15. The light emitting apparatus according to claim 14, wherein the light control element and the field-effect type transistor are integrated.

16. A display apparatus using a light emitting apparatus according to claim 14.

17. A sputtering target comprising indium, tin, zinc, a IIIB group element other than indium (at least one selected from B, Al, Ga and Tl) and oxygen, wherein atomic ratios of the number of indium atoms ([In]), the number of tin atoms ([Sn]), the number of zinc atoms ([Zn]) and the number of atoms of the IIIB group element ([IIIB]) are:

0.1<

[In]/([In]+[Sn]+[Zn])<

0.5

0.1<

[Sn]/([In]+[Sn]+[Zn])<

0.2

0.3<

[Zn]/([In]+[Sn]+[Zn])<

0.8

0.0001<

[IIIB]/([In]+[Sn]+[Zn]+[IIIB])<

0.33, and

wherein a bulk resistance is 10<sup>−

3</sup> to 10³ mΩ

, and a sintered density is 80% or more.

18. A sputtering target comprising indium, tin, zinc, a lanthanoid series element (at least one selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) and oxygen, wherein atomic ratios of the number of indium atoms ([In]), the number of tin atoms ([Sn]), the number of zinc atoms ([Zn]) and the number of lanthanoid series atoms ([Ln]) are:

0.1<

[In]/([In]+[Sn]+[Zn])<

0.5

0.1<

[Sn]/([In]+[Sn]+[Zn])<

0.2

0.3<

[Zn]/([In]+[Sn]+[Zn])<

0.8

0.0001<

[Ln]/([In]+[Sn]+[Zn]+[Ln])<

0.1, and

wherein a bulk resistance is 10<sup>−

3</sup> to 10³ mΩ

, and a sintered density is 80% or more.